The reaction of BiCl3 and VO(OiPr)3 in 2-methoxyethanol resulted in the formation of the first bismuth-transition metal bimetallic alkoxide, [BiCl3(mu-O)(mu-OC2H4OCH3)(2)(OC2H4OCH3)V](2). The vanadium atom is in an unusual distorted octahedral coordination environment, while the coordination around the bismuth is best described as an octrahedron capped by a long bonded interaction with an oxygen atom. There does not appear to be a stereochemically-active lone pair present on the bismuth atom.