Liverpool will have the chance to avenge last season's Champions League final defeat at the hands of Real Madrid after Jurgen Klopp's side were drawn on Monday to face the holders again in the last 16.
Meanwhile, the other standout tie saw Paris Saint-Germain drawn to play Bayern Munich in a repeat of the 2020 final which was won by the German club.
Liverpool won five of their six group games but missed out on top spot to Napoli after losing 4-1 when the sides met in Italy.
The Anfield club also lost the 2018 Champions League final to Real, who won their group ahead of RB Leipzig.
"They are two historic teams and the tie is going to be electric, fascinating for the fans," said Emilio Butragueno, a great former Real player who is now the director of institutional relations for the 14-time European champions.
Current domestic form suggests Real should be favourites, with Carlo Ancelotti's side unbeaten in La Liga while Liverpool are eighth in the Premier League despite winning away to Tottenham Hotspur on Sunday.
However, both clubs will lose key players to the World Cup and Butragueno acknowledged much can change in the three months before the Champions League returns.
"The World Cup is going to condition the whole season. We will see how the players are when they return," he said.
PSG only missed out on topping their group because Benfica scored more away goals across all matches after the sides remarkably finished level on points, goal difference, goals scored and head to head.
