PSA finance chief Jean-Baptiste de Chatillon, who helped oversee a revival of fortunes at the automaker, will leave the automaker to join French pharmaceutical company Sanofi.
He will be succeeded on August 1 by Philippe de Rovira, currently finance boss at of PSA's Opel/Vauxhall unit.
"I would like to thank Jean-Baptiste de Chatillon for his action during these years for the recovery of the company, and his contribution to the new dynamic of Groupe PSA," Louis Gallois, chairman of the PSA supervisory board, said in a statement.
PSA had posted a series of record earnings results over the last two years, having rebounded from a 2012 brush with bankruptcy, and de Chatillon had been a member of PSA's managing board since 2012.
Sanofi said de Chatillon would become its executive vice-president and chief financial officer, effective October 1.
Reuters contributed to this report