Abstract A simple procedure for the preparation of phosphoryl chlorofluorides, POFCl 2 and POF 2 Cl, by chlorination of the appropriate potassium fluorophosphates, K 2 PO 3 F and KPO 2 F 2, respectively, with PCl 5 is described. The analogous bromination with PBr 5 gives POFBr 2 and POF 2 Br. However, due to low yields and high content of impurities, this method is not suitable for the synthesis of the former compound. Both chlorofluorides were ...