The Reds kick off their European campaign on the back of an unbeaten start to the 2026/27 Premier League season as Diego Simeone's LaLiga giants land at Anfield.
In what could be Van Djik's final season at Liverpool, with his contract up next summer, the Dutchman was clear over what's at stake in his programme notes.
"The Champions League is a competition that everyone involved with this club holds dearly, and we can't wait to get our campaign underway this evening.
"When you play for Liverpool, these are the nights you live for, challenging yourself against the best teams and the best players."
Van Dijk scored a last-gasp winner as Liverpool beat Atleti 3-2 at home in the UCL league phase last season after winning two and losing two of his previous clashes with Simeone.