Functionalization reactions of the refrigerants HFO‐1234yf (2,3,3,3‐tetrafluoropropene) and HFO‐1234ze (1,3,3,3‐tetrafluoropropene) were developed. The selectivity and reactivity towards CF3 groups of C−F activation reactions can be controlled by employing either a germane or a silane as the hydrogen source. Unique transformations were designed to accomplish consecutive hydrogermylation and C−F activation steps. This allowed for an unprecedented transformation of an olefinic C−F bond into a C−H bond by heterogeneous catalysis. These reactions are catalyzed by nanoscopic aluminum chlorofluoride (ACF) under very mild conditions. Functionalizations of tetrafluoropropenes such as HFO‐1234yf were developed. The transformation of the CF3 group into an olefinic CF2 group was achieved at nanoscopic aluminum chlorofluoride (ACF) with silane. Consecutive hydrogermylation and C−F activation steps enabled the transformation of an olefinic C−F into a C−H bond.