There was a crushing inevitability about Barca's third European Cup triumph in six years in May and they appear to have an even stronger squad this term following the signings of Cesc Fabregas and Alexis Sanchez.
Yesterday witnessed the draw for the group stage of Europe's premier club competition, with Chelsea and the Catalans kept apart due to their status as top seeds.
But the chances are that if Villas-Boas is to end Roman Abramovich's long wait for Champions League glory, he will have to get past Barcelona at some stage.
And the new Chelsea boss has insisted he would have no fears about pitting his wits against one of the best club sides of all time.
"Barcelona are the reference," he said.
"They can beat any team in the world, but so could Chelsea and so could Real (Madrid).
"If I didn't believe that, I'd quit the game.
"I'm not going into the game with a losing mentality."
Chelsea managed to get the better of Barca more than once while Villas-Boas was part of Jose Mourinho's backroom team, while Mourinho's Inter Milan also beat them two seasons ago.
And Villas-Boas pointed out the competition was littered with upsets, including when he helped Porto triumph in 2004.
"That's what happened with Porto and Monaco," he said.
"Porto put out Deportivo and Lyon, and (Manchester) United in the last 16. Monaco put out Chelsea and Real Madrid.
"It's pretty unpredictable. There's a pattern over the last four years with more or less the same teams present in the semi-finals, but it depends on the draw up to then."
Chelsea have become Champions League ever-presents in the Roman Abramovich era, a feat Manchester City are looking to emulate as they embark on their maiden season in the competition.
Villas-Boas sees them as automatic contenders, saying: "They have joined together the best talent in the world this year.
"It's something unbelievable. It shows what they want to achieve, and they have a winning coach as well, a coach who won three titles in a row at Inter.
"I don't see why they wouldn't have the drive or the qualities to go all the way through."
Villas-Boas played down the similarities between City and the Chelsea he joined under Mourinho seven years ago.
"When we arrived, we were going for talent breaking through," said the Portuguese, who is employing a similar philosophy in his own managerial career.
"(Arjen) Robben, Didier (Drogba), (Ricardo) Carvalho, Paulo (Ferreira).
"City are going for proven talent. (Samir) Nasri and (Sergio) Aguero. They already have their value.
"That shows that, this year, they already want to make a difference.
"They join an elite group that wants to be champions from the scouting and investment that we've seen there."
Champions League Group Stage
|Group A||Group B||Group C||Group D|
|Bayern Munich||Trabzonspor||Manchester United||Olympique Lyonnais|
|Manchester City||LOSC Lille||FC Basle||Dinamo Zagreb|
|SSC Napoli||CSKA Moscow||Otelul Galati||Real Madrid|
|Group E||Group F||Group G||Group H|
|Valencia||Arsenal||Zenit St. petersburg||BATE Borisov|
|Bayer Leverkusen||Olympique Marseille||Shakhtar Donetsk||AC Milan|
|Racing Genk||Borussia Dortmund||APOEL||Viktoria Plzen|