The Reds marched all the way to the final in 2017-18, only to fall to a cruel 3-1 loss at the hands of perennial winners Real Madrid in the Kiev final.
Four months on from that setback, Jurgen Klopp has to navigate his side through a tough group that contains French champions PSG, Serie A runners-up Napoli and Serbian giants Red Star Belgrade.
Here, Sports Mole looks at how the Merseyside outfit may set up for their opening Group C clash.
Out: Dejan Lovren, Adam Lallana, Alex Oxlade-Chamberlain
Doubtful: Divock Origi, Dominic Solanke, Roberto Firmino
Liverpool's biggest concern ahead of this tricky opening assignment is the fitness of forward Firmino, who left the field early against Tottenham Hotspur at the weekend because of a nasty eye injury.
Speaking on the eve of the PSG showdown, Klopp was unable to confirm whether Firmino will be cleared in time to feature, but he will give the Brazilian every possibility.
Fringe players Origi and Solanke are both carrying knocks, meaning that Daniel Sturridge is the obvious candidate to replace Firmino in the forward line if worse comes to worst, alongside Mohamed Salah and Sadio Mane.
Changes are otherwise expected to be kept to a minimum, with summer signing Fabinho being made to bide his time on the substitutes' bench.