The monosolvate (MeCN) of niobium(V) chloride has been structurally characterized. The metal is six coordinate with a somewhat distorted octahedral geometry in which the four equatorial chlorine atoms are coplanar but are clearly bent towards the bound axial acetonitrile ligand, mean N a x --Nb--Cl e q 83.62(12)°. The Nb--Cl bond distances lie in the range 2.249(2)-2.319(2) and the metal to ligand distance, Nb--N, is 2.236(4) .