The Blues cut through their opponents' defence at will in the first half at the Reebok Stadium, with Frank Lampard and Daniel Sturridge - scorer of eight goals in 12 games during a loan spell with Wanderers last season - both netting twice.
Three and easy: Lampard netted a stunning hat-trick in the win over Bolton
Sturridge put the visitors in front in the second minute, teed up Lampard in the 15th and the London side then raced into a 4-0 lead with less than half an hour of the contest gone.
Dedryck Boyata pulled one back for Bolton a minute into the second half, but it counted for little as Lampard completed his hat-trick just before the hour mark to wrap up the thumping win, Chelsea's most emphatic since Villas-Boas was appointed as manager in the summer.
The Portuguese was delighted to see his side being so clinical, having felt they had been threatening such a scoreline with the amount of chances they were creating in recent weeks.
At the double: Sturridge scored two goals in Chelsea's 5-1 victory
'We have been chasing this victory and think we have deserved it for quite some time,' Villas-Boas said.
'It is just something that fills us with pride because it is not as if we have not been trying to do this before.
Content: Villas-Boas was pleased with Chelsea's performance
'We have, but football is a game full of uncertain things and for various different reasons - luck, or lack of efficiency - we were not able to find a result with this expression before.
'But I think in all of the games we have been creating the same amount of opportunities, and here we were just more prolific.'
It meant Chelsea went back up to third in the Barclays Premier League table and are once again three points away from pace-setters Manchester United and Manchester City.
Bolton, meanwhile, stay rock bottom, with their losing streak in the league extending to six games.
Their defending was generally poor, with goalkeeper Adam Bogdan - in the Trotters team for the injured Jussi Jaaskelainen - enduring a particularly bad afternoon, letting Sturridge's shot from the edge of the box loop in off him in the 25th minute when he should have saved, and then two minutes later, parrying David Luiz's strike straight at the feet of Lampard.
Bolton manager Owen Coyle expressed his sympathy for the Hungarian stopper.
'Young Adam Bogdan is going to have a terrific career, there is no doubt about it, Coyle said.
But the third and fourth goals should have been basic saves and that is the thing with a goalkeeper - there is no hiding place if they make a mistake, it results in a goal.
'I feel for the kid, but he has to show the character to come through that.'
Bolton 1 Chelsea 5: Three and easy for Lampard as five-star Blues run riot Defender Bosingwa back in favour and poised to extend stay at ChelseaSportsmail's Match Zone: All the stats, facts and fallout from Saturday's games