The methathesis reactions between NbCl 5 and lithium-2,6-dimethylphenoxide, LiO-2,6-PhMe 2 , afford LiNbO(O-2,6-PhMe 2 ) 4 .3THF (1) and [LiNbCl 3 (O-2,6-PhMe 2 ) 2 .2THF] 2 (2). The complexes 1 and 2 were characterized by X-ray single crystal diffraction analyses, elemental analyses, and FT-IR, 1 H and 1 3 C NMR spectroscopy. Complex 1 exists as a monomeric binuclear lithium niobium complex which has a terminal oxo ligand, and complex 2 exists as a dimeric tetranuclear lithium niobium complex where metal atoms are linearly connected by μ 2 -chloride linkages, respectively. Lithium metal is coordinated by THF molecules as a counter ion.