Reaction of the trivanadium-substituted polyoxometalates (Bu4N)7SiW9V3O40 and (Bu4N)9P2W15V3O62 with an equimolar amount of CpTi3+ leads to the formation of the polyoxometalate-supported organometallic complexes [CpTi.SiW9V3O40]4-, 1, and [CpTi.P2W15V3O62]6-, 2, respectively. These Complexes were isolated salts and subsequently characterized by a complete elemental analysis and P-31, W-183, V-51, and H-1 NMR spectroscopy as well as FAB-MS, IR, and sedimentation-equilibrium molecular-weight measurements. For compound 1 additional data in the form of 2-D INADEQUATE W-183{V-51} NMR spectra were collected. Both 1 and 2 are homogeneous, regiospecifically supported CpTi3+ complexes of overall C(s) symmetry. Solution structures, derived from and in accord with the observed spectroscopic data, are proposed. The synthesis and initial solution spectroscopic characterization of the non-cyclopentadienyl, ClTi3+ complex, ClTi-SiW9V3O404-, is also reported, a nominally highly coordinatively unsaturated Ti(IV) complex on route to more reactive catalyst precursors.