The Italian head coach confirmed the appointment in his pre-match press conference on Friday, naming Van de Ven at the head of a five-man leadership group that also includes Pedro Porro, Ben Davies, James Maddison and Archie Gray.
"The new captain is Micky van de Ven. The second Pedro Porro, the third Ben Davies, the fourth James Maddison and the fifth Archie Gray," De Zerbi told reporters, explaining that he wanted several senior voices on the pitch rather than relying on a single armband holder.
Van de Ven, 25, is no stranger to the responsibility, having led the side on several occasions last season, including throughout Tottenham's run-in as they secured Premier League survival while Romero was sidelined through injury.
He was also part of the squad that won the UEFA Europa League in 2025, a campaign in which he produced a crucial goal-line clearance against Manchester United in the final.
"It's a massive honour to be captain of Tottenham Hotspur," Van de Ven said.
"This is a massive club, and to have the responsibility to lead the team out of the tunnel every game, wearing the armband, is something you dream of."
The new captain will not get the chance to wear the armband immediately, however. Van de Ven is set to miss Saturday's Premier League opener away at Brentford after picking up a minor knock during pre-season, with De Zerbi confirming both his new captain and vice-captain Pedro Porro will be unavailable for the trip to west London.
Marcos Senesi and Ben Davies are expected to deputise at the back in their absence as Tottenham begin the defence of last season's survival with a squad freshly strengthened by the arrivals of Sandro Tonali, Mateus Fernandes and Jan Paul van Hecke.