Xavi thinks Frenkie de Jong is "one of the best midfielders in the world" and will hand him the captain's armband for the Netherlands' Nations League clash with Greece.
Virgil van Dijk usually captains the Oranje, but he is currently sidelined through injury.
It is a big blow for the Netherlands, who are also missing striker Brian Brobbey, though they are boosted by the return of De Jong, who has not played for them since the World Cup, when he suffered a knee injury.
He was one of Xavi's key players at Barcelona, winning a LaLiga title under him in 2022-23, and the Spaniard see the midfielder as a key part of the national team.
As such, De Jong will lead the team out against Greece on Friday, with Denzel Dumfries and Cody Gakpo named as vice-captains.
"We decided this on Monday," Xavi said. "Frenkie has a good personality.
"He wants the ball and wants to get better every day. He always takes responsibility. He is one of the best midfielders in the world, if you ask me.
"Virgil is a good leader; he is a top player. But it is no excuse for [the Greece clash]. We have many good options."
Things are very tight in the Netherlands' group, with Greece level with them on eight points and only below Xavi’s side due to scoring fewer goals.
Germany are third in the group, with five points, and they face the Netherlands in the final game on November 16, meaning a result against Greece could be key for Xavi’s side.