Two complexes containing both vanadium and lithium, [V6Li10O8(ONep)14{O2Si(Me)2(ONep)}2] (1) and [V(ONep)3(µ-ONep)2Li(thf)2] (2), Nep = neopentyl, Me = methyl and thf = tetrahydrofuran, have been isolated in high yield and characterised by a number of techniques including X-band electron paramagnetic resonance (EPR) and 29Si{¹H} nuclear magnetic resonance (NMR) spectroscopies, magnetic susceptibility measurements and single crystal X-ray diffractometry. Despite the similar preparation conditions, the two products present remarkably distinctive structural features: complex 2is a binuclear adduct of "V(ONep)4" and "Li(ONep)(thf)2", while 1is a mixed-valence, 16-metal aggregate. The large molecular oxoalkoxide 1also contains silanolate units, {OSi(Me2)(ONep)} -, produced by nucleophilic attack of neopentoxide groups on Si-O bonds of silicone grease accidentally dissolved in the reaction media. Both products have promising applications in organic and inorganic synthesis, including the preparation of uncommon V-Li and/or Si containing oxides.