Herein, we report an efficient iridium-catalyzed double asymmetric hydrogenation of 2,5-dialkylienecyclopentanones, delivering the chiral 2,5-disubstituted cyclopentanones in excellent yields and stereoselectivities. The results of the kinetic experiments and control experiments indicated that the two C═C bonds were hydrogenated in a stepwise manner and the second stereocenter was synergistically controlled by the chiral catalyst and the chirality of monohydrogenated product. The hydrogenated products can be prepared on a gram-scale and are easily derivatized.