(Arylimido)vanadium(V) triisopropoxides, [(p-RC6H4N)V((OPr)-Pr-i)(3)] (R = NMe2, OMe, H, CN, NO2, Br), were prepared by the reaction of VO((OPr)-Pr-i)(3) with the aryl isocyanates without solvent. The structures of the (arylimido)vanadium(V) triisopropoxides were characterized by single-crystal X-ray structure determination to elucidate the substituent effect on the self-association properties. Controlled association of the (arylimido)vanadium(V) triisopropoxides to the mu-oxo-bridged dimer complexes or the mu-imido-bridged dinuclear complex was achieved by changing the p-substituent on the benzene rings, which regulates the nature of the imido bonds. Furthermore, the one-dimensional linear polymer complex or the one-dimensional zigzag one through mu-oxo-bridging was formed in a solid state with the bimetallic (arylimido)vanadium(V) complex, [((PrO)-Pr-i)(3)V(N-p-C6H4N)V((OPr)-Pr-i)(3)] or [((PrO)-Pr-i)(3)V(N-m-C6H4N)V((OPr)-Pr-i)(3)], respectively.