Chelsea were criticised for being cautious under Jose Mourinho but Scolari's first match in charge suggested he wants style as well as substance, and they continued to push forward once Joe Cole opened the scoring in the 12th minute.
Nicolas Anelka, Scolari's only senior forward available, headed in his first goal at home for Chelsea before Frank Lampard put the result beyond doubt just before the break, scoring a penalty just five days after sealing his new five-year contract at the club.
• Scolari: This is just the start
Deco, on his debut, added a fourth from long range just before the end.
While Lampard may have been in the headlines this week it was Scolari - wearing a blue club tracksuit - who took centre stage on the opening weekend of the new season.
The Brazilian had promised a samba style to his time in west London, and he did not disappoint after being introduced to the crowd and giving them a thumbs-up.
Like his Brazil team that won the 2002 World Cup, he relied on his full-backs to create width - instead of Cafu and Roberto Carlos he has Jose Bosingwa and Ashley Cole marauding forward.
It allowed his five-man midfield to dominate through the middle, which is where the opener was created from less than a quarter of an hour into Scolari's career in England.
Anelka cushioned a header back to Michael Ballack, who lifted the ball over Pompey's defence with the outside of his boot for midfielder Cole to steer his finish around David James.
It could have got worse for the visitors as Lampard split their defence again, only this time James saved with his feet when Anelka ran through.
The France striker was not made to wait long for his goal. Bosingwa helped set it up by getting to the byline and standing up a cross to the far post.
Ballack almost got in the way as Deco met the ball but the Portugal midfielder managed to clip over James and Anelka beat Sylvain Distin on the line to head into the empty net.
Anelka should have added a third on the half-hour mark when he raced through again, but his effort went just wide of the post after he tapped the ball around James.
It did not run entirely smoothly for Scolari as he was forced into a change when Ballack picked up a knock, with Florent Malouda coming on.
Pompey also suggested they were willing to fight back when Petr Cech was forced into a double save before the break, first from Niko Kranjcar's powerful drive, then bravely with his body when Peter Crouch latched onto the rebound.
However, their hopes ended when Chelsea were awarded a penalty in first-half stoppage-time after Distin handled a cross by midfielder Cole.
James was booked for kicking the ball away before Lampard tucked away the spot-kick and tapped his badge in celebration as he ran to the crowd.
Pompey boss Harry Redknapp, Lampard's uncle, had offered his advice before Lampard committed his future to Chelsea - and there was an inevitability that the midfielder would find the net against his relative.
The attacking continued after the break, with Anelka twice firing over the crossbar after the restart.
Midfielder Cole went sent through over the top again but fired wide of the post after outpacing the Pompey defence.
Pompey, in contrast, looked short on belief and were contributing to their own downfall, one free-kick in their own territory resulting in possession lost and a chance being presented to Anelka.
Younes Kaboul thought he had sight of goal from a corner but his effort came off his knee, and Crouch could not tame the ball when it fell to him.
Pompey also had a penalty appeal when Niko Kranjcar's drive was blocked by Ricardo Carvalho.
Crouch's partnership with Jermain Defoe clearly needs time to gel. It took them 78 minutes to combine, and Defoe could not get direction on his finish when he met a flick-on.
Deco's goal came in the 89th minute, a powerful and swerving effort from 30 yards that James could only parry into the top corner.
Scolari: This is just the start
Big Phil Scolari was impressed by his new charges but insisted there is more to come.
'I'm happy because my team play very well,' the Brazilian told Sky Sports
News. 'To win the first game 4-0 is important but more important for me is my
team looked well in the field and I think the Chelsea fans are the same.
'We still need more patience and to touch the ball more. We expect more goals
but at 3-0 we need to change to keep the ball more.'
The one negative for Chelsea was an injury to Michael Ballack, who had to go
off during the first half with an ankle problem.
It will be a concern for Scolari because Ballack missed a large chunk of last
season following ankle surgery. He could now miss Germany's friendly with
Belgium on Wednesday.
Scolari explained: 'He played very well but he had something in his ankle and
he tried a second time but it was impossible to continue.
'Now we have to discuss Ballack with the national team from Germany. The
doctor said it is impossible to say whether it is a problem or not for the
future.
'We hope next Wednesday or Sunday he's in good condition but it's
difficult.'
Frank Lampard declared the first 45 minute was 'as good as we can play'.
Lampard told Sky Sports News: 'We just wanted to play as well as we can. We
wanted to start all guns blazing. Last year we had a difficult start and the football we played in the first
half today was top drawer.
'We can build on that. The first half was as good as we can play. Having not won anything last year we go in (to this season) with a real
determination and I think we showed that.'
Lampard singled out the performance of Portugal midfielder Deco following his
summer transfer from Barcelona.
'It was a brilliant start,' added Lampard. 'It's not easy to come to a
different country and settle in as quickly as he has. His touch is fantastic and
he's obviously going to be a great signing for us.'
Deco seemed pleased with his first competitive game for the Blues, adding on
Sky Sports: 'I feel good, it was a great game. To start with a win is the
important thing.'
Pompey boss Harry Redknapp is looking for more signings before the end of the
transfer window but admitted he needed to sell Pedro Mendes to Rangers this week
to balance the books.
'Where do you get good loans? I'd like to try, but it's not easy,' he said.
Redknapp feels Chelsea's performance proves it is impossible for clubs outside
the traditional top four to break into the Champions League places.
He said: 'You're not going to break into the top four. No-one is this year. Spurs have got a squad and can't even win at Middlesbrough, so you start
forgetting about them.
'The top four are on another level. We've improved the standard of the squad
in the last three or four years but, today, you step up into a different
level.'
Despite his frustrations, Redknapp insists he does not want to move from
Fratton Park, despite recently being linked with a return to West Ham.
He added: 'I've had opportunities before and didn't take them. I'm happy where I am. It's not a case of the grass being greener.
'We'll do better than that, for sure. We've got an easy game next Monday
against Manchester United.'
Chelsea 4 - 0 Portsmouth
