MoO2F2 is prepared by pyrolysis of (Na+H2O)(2) cis-MoO2F42-. A preliminary model of the structure is obtained from powder data: it has a triangular columnar structure with three fluorine bridges between the three molybdenum atoms and with oxygen bridges between the layers (a = 1605, b = 384, c = 1395 pm, Pnma, Z = 12) The closest related structure is that of TiF4, except that the orientation of the triangular columns is different