Holders Manchester United will face 2004 winners Porto in the Champions League quarter-finals after the draw at Uefa headquarters.
|Exciting times ahead in the Champions League [AFP]
Liverpool and Chelsea will meet for the fifth successive season in the competition.
The English Premier League clubs have met three times in semi-finals in the last four years and also in the group phase.
Liverpool prevailed in 2005 and 2007 but the Londoners finally overcame their bogey team in extra-time last season before losing to United in the final.
Barcelona meet Bayern Munich while Villarreal will play Arsenal in the other last-eight ties. Arsene Wenger's team beat the Spaniards in the 2006 last four before losing to Barca in the final.
The quarter-final first legs will be played on April 7 or 8 with the return matches the following week.
In the semi-finals, United or Porto will play Villarreal or Arsenal and Barcelona or Bayern will meet Liverpool or Chelsea.
The semi-finals take place on April 28 and 29 and May 5 and 6.
Liverpool, buoyed by Benitez's contract renewal and their drubbings of Real Madrid and Manchester United, will play their second leg at Stamford Bridge on April 14, so avoiding having to play on April 15 - the 20th anniversary of the Hillsborough disaster.
"There's nothing we don't know about them, we probably know the inside leg measurement of Rafa's trousers," Chelsea secretary David Barnard said of the clash that will make it 24 meetings in all competitions in five seasons between the Premier League rivals.
"In theory having the second leg at home should help us," he told Britain's Sky Sports News.
"It worked last year while in the previous two years Liverpool were at home second and got through."
Liverpool chief executive Rick Parry felt the order of home advantage was less of an issue and that there was greater concern about the date.
"We do not want to play on the 15th, it's massively important to the club and to every Liverpool fan," he said.
"There is no more important issue for Liverpool football club."
Parry is leaving Liverpool at the end of the season after 11 years and said: "We started off in the Uefa Cup draw wishing we were in the other room with the big boys, now we are regularly so it's great to still be here."
Arsenal chief executive Ivan Gazidis said he hoped for less tension than when Arsenal got past Villarreal in 2006 after Jens Lehmann's last-minute penalty save.
Villarreal v Arsenal
Man United v Porto
Liverpool v Chelsea
Barcelona v Bayern Munich
First legs April 7 and 8
Second legs April 14 and 15
Manchester United or Porto v Villarreal or Arsenal
Barcelona or Bayern Munich v Liverpool or Chelsea
First legs April 28 and 29
Second legs May 5 and 6
"We just squeezed by on a 1-0 aggregate then, I hope it's not quite so dramatic this time," he said.
"We respect Villarreal and they are here on merit.
"We believe in the quality and the character of our team and I think you saw a bit of that in a difficult environment in Rome.
Villarreal were playing their first season in the Champions League when they were beaten by Arsenal and president Fernando Roig said: "We have a bit more experience than last time, maybe then we were a bit of a surprise then."
United lost to eventual winners Porto in 2004 when Jose Mourinho was the coach of the Portuguese side.
Alex Ferguson got his own back on his old nemesis last week when United knocked out Mourinho's Inter in the last 16 and United secretary Ken Ramsden said he thought Ferguson would be happy with the draw.
The final will be played on Wednesday, May 27 at the Stadio Olimpico in Rome, where there will be no home interest after Inter, Juventus and AS Roma were all eliminated in the last 16.