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. Funktionalisierungen von Tetrafluorpropenen wie HFO‐1234yf wurden entwickelt. Die Umwandlung der CF3‐Gruppe in eine olefinische CF2‐Einheit gelang mit nanoskopischem Aluminiumchlorfluorid (ACF) und einem Silan. Aufeinanderfolgende Hydrogermylierung und C‐F‐Aktivierung ermöglichten die Umwandlung der olefinischen C‐F‐Bindung in eine C‐H‐Bindung.