The fluoridolysis of various P-Cl-, P-O-, and P-N-compounds such as PCl 5, R 3−nPCl n, X 3−nCl nPNPOCl 2 (X = OPh, Ph; n = 0 − 3), Cl 2P(O)NHP(O)Cl 2, acyclic and cyclic esters and amides of phosphorous acid with organyl- ammonium fluorides, e. g. Et 3N·nHF, has been investigated. As a result convenient methods for the preparation of organylfluorophosphanes, R 3−nPF n, [1] several fluorophosphates, [XPF 5] − (X = H, RO), and F 2P(O)NP(O)F 2 − have been developed. Due to the high nucleophilicity and concentration of the fluoride ions, fluorophosphates are formed preferably: [X nPF 6−n] −: X = F; Cl (n = 4, 5); RO (n = 1−4); H (n = 1); RNH (n = 1). Even an exchange of phosphoryl oxygen by fluoride takes place under certain conditions (e. g. in POCl 3 and (PhO) 2PClNPOCl 2). In the case of N-phosphorylated phosphazenes, X 3−nCl nPNPOCl 2 with X = OPh and Cl the fluoridolysis effects a cleavage of the PNP-bridge. [(PhO) 2PFNPF 5] − has been detected as intermediate. However, in Ph 3PPOCl 2 and imidodiphosphoryl compounds the PNP-bridges are stable against fluoride. The factors affecting the course of fluoridolysis reactions and the kind of the reaction products (neutral compounds or hexacoordinated anions) are discussed.