Team Europe head into the event at London's O2 Arena as the favourites in the eyes of many, almost entirely due to the presence of Alcaraz and Zverev.
Alcaraz's talent and credentials need no explaining, while Zverev's stock has risen hugely in the last year, with the German winning his first two Grand Slam titles at the French and US Opens.
However, the Spaniard doesn't see himself as the leader of the team, despite being its most high-profile and accomplished member by some distance.
"I think, in this team, there's no leader," he said at the pre-tournament press conference. "I'm serious.
"In this team, everybody is (one of) the best players in the world... We're all trying to help each other in the best way we can.
"So I'm not seeing me as a leader, not only in this competition but in any of them. I'm just trying to do my best and help teams as best as I can."
Zverev has played in each edition of the Laver Cup, but this is the first time that he's entered it as a Grand Slam champion.
However, he doesn't think that changes a huge amount in regard to his role within the team.
"Yes and no," he said to the suggestion that this year's tournament has a different feel for him.
"Because at the end of the day, I think we have great champions in this team. We all know what it takes to win.
"Of course, for me personally, it was quite a satisfying year, but we're here at the Laver Cup as a team. The main goal is to lift the Laver Cup trophy and bring the Laver Cup trophy back to Europe, and we do it as a team, we do it as a group of players, and hopefully we can achieve that goal."