He joins the Toffees on a two-year contract, with the option for a further season.
“I am really, really happy to be at this great club, a club with so much history, and here with a manager who knows me really well,” said Rodriguez.
“I’m looking forward to achieving great things here – and winning things, which is what everyone’s aim is.
“I’ve come here to try to improve, to get better. I’ve also come here to help the team to win, to play good football – entertaining football.”
James Rodriguez, who was entering the last year of his contract with the Spanish champions, featured 14 times for Zinedine side last season.
It is the third time he has been signed by Everton boss Carlo, having joined the Italian at Real Madrid and Bayern.
“I’m convinced, with Carlo and his technical staff, we can achieve big things and one of the big reasons [I signed] was the presence of Carlo Ancelotti,” Rodriguez added.
“I have enjoyed some great times with him previously at two different clubs. That was a massive reason to come here.”
Ancelotti said: “James, as everyone knows, is a fantastic player with a lot of quality and a lot of ability to make assists for the strikers.
“He’s really excited about the project of the club and the fact we want to improve. He was really excited to sign and I didn’t spend time to convince him – he was already convinced.”
Rodriguez is part of an ambitious Ancelotti rebuilding program at Everton, with the Toffees having signed Napoli’s combative Brazil international Allan and agreed on a fee for Watford’s French midfielder Doucoure.
The Colombian has been marginalized under Zidane at the Bernabeu and was allowed to miss pre-season training to sort out his future.