MoO(2)F(2) is prepared by pyrolysis of (Na(+)H(2)O)(2) cis-MoO(2)F(4)(2-). 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 TiF(4), except that the orientation of the triangular columns is different.