Jimenez has featured in four Ryder Cups as a player and three as a vice-captain, and James, who gave the Spaniard his playing debut in the competition in 1999, believes that he is the man to wrest the trophy back from the Americans.
"If Miguel Angel Jimenez wants to be the next European Ryder Cup captain, he's the man the selection panel should go for," James told ESPN.
"There's no question that he would make a brilliant leader, and I think he'd be better in Paris in 2018 than in Wisconsin two years later because he is a little extroverted, and it's easier to be that way at home.
"Jimenez has done everything you can except win majors in the European game. He has won 21 tour titles, is highly respected by his fellow players and is well-liked. He has to be the number one candidate. Beyond Jimenez, Lee Westwood and Thomas Bjorn would be good candidates, and Europe is lucky there are some great options."
Jimenez was a vice-captain in 2012 and 2014 and most recently played in the tournament at Celtic Manor in 2010.