New heterometallic alkoxides [LiNb(OCH 2 CMe 3 ) 6 ] 2 (4), LiNb(OCH 2 CMe 3 ) 6 (Me 3 CCH 2 OH) 2 (5), and [LiNb(OCH 2 SiMe 3 ) 6 ] 2 (6) have been prepared from the corresponding homometallic alkoxides. All are moderately soluble in hydrocarbons and sublime in moderate to good recoveries. The structure of 6 determined crystallographically contains an Nb 2 Li 2 (μ-O) 4 (μ 3 -O) 2 central-core geometry. Compound 4 appears to be isostructural on the basis of 1 H NMR data. Bulk pyrolysis of 4 gives crystalline LiNbO 3 under N 2 at 600 o C. However, LiNbO 3 films are not obtained from 4 by spray MOCVD under conditions that give LiNbO 3 films from [LiNb(OEt) 6 ] ~ . Crystallographic structure determination for the precursor compound [Nb(μ-OCH 2 SiMe 3 )(OCH 2 SiMe 3 ) 4 ] 2 (3) reveals an edge-shared biotahedral geometry in which the μ-O atoms are distinctly pyramidal. This structure is maintained in solution; the pyramidal bridge configurations allow coexistence of syn and anti dimeric isomers. Precursor 3 also exhibits a dimer-monomer equilibrium for which ΔH = 63(3) kJ/mol and ΔS = 180(10) J/(K mol).