Commercially available BiPh 3 was treated with perfluoroalkylphosphinic acids [for example, (C 2 F 5 ) 2 P(O)OH] to generate novel, highly Lewis acidic bismuth(III) perfluoroalkylphosphinates of the type Ph x Bi[RF 2 PO 2 ] 3−x (x=0, 1, 2) (RF=‐C 2 F 5 , ‐C 4 F 9 ). The first bismuth(V) perfluoroalkylphosphinate, Ph 3 Bi[(C 2 F 5 ) 2 PO 2 ] 2 , was synthesized from Ph 3 BiCl 2 and Ag[(C 2 F 5 ) 2 PO 2 ]. Examples for the successful application of the catalytically active bismuth(III) and bismuth(V) phosphinates in carbon–carbon bond forming reactions, such as Friedel–Crafts acylation and alkylation, Diels–Alder, Strecker and Mannich reaction, are presented.