Already champion in the discipline in 2007, Pitel crossed the line alone ahead of Marjolaine Bazin and Audrey Cordon-Ragot after clocking 3hr 6min 11sec over 104.8km.
Pitel adds to the silver she won in Thursday's time-trial event behind Cordon-Ragot and ahead of Delzenne. Pitel won the time-trial in 2004 and 2005.
Two-time French champion Pauline Ferrand-Prevot just missed out on the podium with Cordon-Ragot winning a sprint for bronze in the competition in eastern France.