Just days after saying he wanted to stay, Montezemolo -- who has been dogged by six years of Formula One racing failure -- announced he will be stepping down on October 13.
The top job at the Italian Ferrari luxury sports car company will be taken over by the head of parent group Fiat, Sergio Marchionne.
A press conference held by Montezemolo and Marchionne was announced for Wednesday afternoon.
But the brand's poor performance over the past six years, combined with recent clashes in strategy between Montezemolo and Fiat, had led racing watchers to tip his likely exit.
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The decision not to appoint Montezemolo to the new board of the merged Fiat Chrysler Automobiles also suggested the Italian businessman was on the way out.
"I want to personally thank Luca for everything he has done for Fiat, for Ferrari, and for myself," he said.
Ferrari is a subsidiary of the Fiat Group which Montezemolo, aged 67, chaired from 2004 until 2010.
His 23 years at the wheel of Ferrari saw the team's drivers win the Formula One title six times, but the last title came in 2007 and the team has struggled since then to compete on the track with the likes of Red Bull and Mercedes.