gem‐Difluorocyclopropanes (F2CPs) have aroused considerable attention not only from the structural perspective but also due to their ability to participate in various valuable transformations. This Review summarizes advances in catalytic ring‐opening reactions of gem‐F2CPs, especially emphasizing the reactivities and applications of those non‐activated ones under transition‐metal catalysis. Their achievements, synthetic applications and limitations are discussed with the aim to stimulate enthusiasm for further development.