Barcelona and Liverpool, the last two winners of the Champions League, will face each other in the first knockout round of the this season's competition following the draw made on Friday.
The first leg will be at the Nou Camp where Barcelona have never beaten, or even scored against Liverpool in three European matches going back to 1976.
"We are the last two European champions and it will be an extraordinary tie between the two teams," Barca president Joan Laporta told Antena 3 television. "They will be very tough rivals and play a physical style of football.
"They also have players that we know very well like Luis Garcia, who played with us, and Xabi Alonso. But we are the team to beat."
Another intriguing tie pits Porto, who won the competition under coach Jose Mourinho in 2004, against Chelsea, where Mourinho is now coach.
The sides met in the competition shortly after Mourinho went to Chelsea in the summer of 2004, with Chelsea winning 3-1 at home in a group match in September 2004 and Porto winning the return 2-1 three months later.
Arsenal, runners-up to Barcelona in last season's final, travel to PSV Eindhoven where Gilberto of Arsenal scored the fastest goal in Champions League history after 20.07 seconds in Arsenal's 4-0 win in a group match in September 2002.
In other ties, Lille face Manchester United, old rivals Real Madrid will play Bayern Munich for the 17th time in European competition, Inter Milan are up against Valencia, AS Roma will meet Olympique Lyon and Celtic will face AC Milan.
The first legs will be staged on February 20-21 next year with the return legs on March 6-7. The final is in Athens in May.
Draw for the Champions League first knockout round:
Porto (Portugal) v Chelsea (England)
Celtic (Scotland) v AC Milan (Italy)
PSV Eindhoven (Netherlands) v Arsenal (England)
Lille (France) v Manchester United (England)
AS Roma (Italy) v Olympique Lyon (France)
Barcelona (Spain) v Liverpool (England)
Real Madrid (Spain) v Bayern Munich (Germany)
Inter Milan (Italy) v Valencia (Spain)
Match dates:
First legs: February 20-21, 2007
Second legs: March 6-7, 2007