K 2 PO 3 F is orthorhombic, space group Pnma, with a = 7.554(4), b = 5.954(5), c = 10.171(6) Å, and Z = 4. Intensity data have been measured on an automatic diffractometer with CuK α radiation. The crystal structure was determined by analogy with that of K 2 SO 4 and shows an important interaction "F---K". The final R index is 0.065 for 353 observed reflections.