River Plate qualified for the tournament in Japan after beating Mexican club UANL in their semi-final of the 2015 Copa Libertadores and are the favourites after European champions Barca.
And Riquelme, who won the Intercontinental Cup with Boca against Real Madrid in 2000, is sure the South American side can cause an upset against his former club Barcelona if they meet in the final
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"I have absolutely no idea how River should play against Barcelona, but I think Argentinean footballers always give something more in these types of games.
"Can they win? Of course they can. It's only one game, but everyone knows how complicated it will be.
"For the River players it's a unique opportunity. It's a final, I'm going to watch it and I'm going to enjoy it."
While Barcelona boast arguably the best attacking trio in world football history, Riquelme elected to praise another Barca trio.
"Barcelona have the three best players in the world in their position; Gerard Pique as centre-back, Sergio Busquets as defensive midfielder and Andres Iniesta as central midfielder," he said.
River will play either Sanfrecce Hiroshima or TP Mazembe in the semi-finals in Osaka on Wednesday, while Barca are set to meet the winner of America versus Guangzhou Evergrande in Yokohama the following day.