The draw, conducted by Gianluigi Buffon, Cristiano Ronaldo, and UEFA's supercomputer, produced heavyweight clashes like Manchester City against PSG and Borussia Dortmund vs. Madrid.
In the revamped format, each team will play eight games before the knockouts, which include two more than previous years, with the final matches on Jan. 29.
Bayern Munich will face Barcelona for the third time in four seasons, having won the last six encounters, including an 8-2 quarterfinal victory in 2020.
Liverpool will host Real Madrid, and Xabi Alonso returns to Anfield with Bayer Leverkusen while Klopp's announcement has sparked managerial discussions.
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