Liverpool finished first in the 36-team league phase of the competition to qualify directly for this stage, while PSG had to come through a two-legged play-off tie in which they crushed fellow French side Brest 10-0 on aggregate.
The first leg will take place at the Parc des Princes in Paris on March 4 or 5, with the return at Anfield a week later.
The clubs last met in the Champions League in the group stage in 2018/19, when PSG won 2-1 at home after Liverpool triumphed 3-2 in England.
Read moreAfter Mbappé: Could PSG’s least ‘galactic’ team be their most successful yet?
In another eye-catching tie, reigning champions Real Madrid will play city rivals Atletico Madrid in a repeat of the finals of 2014 and 2016, both of which were won by Los Blancos.
Bayern Munich will take on German rivals Bayer Leverkusen, while Arsenal face PSV Eindhoven and Inter Milan take on Feyenoord, who are fresh from knocking out AC Milan in the play-offs.
Barcelona will face Benfica, who they defeated 5-4 away in Lisbon in the league phase last month.
Aston Villa will face Club Brugge, having already lost away to the Belgians in the league phase.
Last season’s beaten finalists Borussia Dortmund will take on French side Lille.
(FRANCE 24 with AFP)
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