Neymar became a Camp Nou idol during his three years at Barcelona before moving to Paris Saint-Germain in a world record transfer.
The Brazilian, however, has long been linked with a possible Madrid switch, having trialled for the Merengue as a youngster.
And according to Rivaldo, the move could yet still happen even with his compatriot's Blaugrana past.
"Neymar to Real Madrid? You never know," he said at an event hosted by Betfair, before adding that he backed the striker's decision to leave Barca.
"He wanted to be the best and he has made the right choice in order to achieve that."
Rivaldo also spoke out on Saturday's Clasico, admitting that he was struggling to pick a winner.
"In a Clasico there are no favourites because Real Madrid have shown they are able to win at Camp Nou and Barcelona know how to do that at the Bernabeu," the ex-Brazil international said.
Rivaldo spent a total of five years at Camp Nou between 1997 and 2002, winning La Liga on two occasions.
The playmaker was also a key part of Brazil's World Cup-winning team in 2002, hitting five goals to finish behind Ronaldo as the tournament's top scorer.