The synthesis and structural determination of three new heterometallic molybdenum complexes, one with cobalt and two with nickel and two of these with -diketonate ligands and one with amino alcohol ligands, are presented. The reaction of cobalt acetylacetonate with [MoO(OMe)4] provides [Co2Mo2O2(acac)2(OMe)10] (1) and [MoO(acac)(OMe)3] (4),and the reaction of nickel acetylacetonate with [MoO(OMe)4]provides [Ni2Mo2O2(acac)2(OMe)10] (2) and 4. The reaction of [Ni(ORN)2] (RN = CHMeCH2NMe2) with [MoO(OMe)4] yields [Ni2Mo2O2(ORN)2(OMe)10] (3). The two new oxomolybdenum complexes undergo ether elimination upon storage to give the corresponding dioxo complexes [MoO2(acac)(OMe)]2 (5) and [MoO2(ORN)(OMe)]2 (6). Compounds 3 and 4 could also be obtained from the reaction of stoichiometric amounts of Hacac with [MoO(OMe)4] and [MoO2(OMe)2], respectively. The local structure around the nickel atom in compound 2 in solution and compound 3 in the solid state and in toluene/hexane solution has been determined by means of EXAFS spectroscopy. The complexes are intended to be used as single-source precursors, which are attractive in coatings and for the preparation of mesoporous materials; its application for the synthesis of nickel molybdate by sol-gel processing is therefore reported. The oxide material obtained from 3 displays a uniform grain size and a large surface area.