Structural characterization of (arylimido)vanadium(V) compounds was demonstrated to elucidate the ligand effect on the nature of the imido bonds. In the case of the triisopropoxide ligand, the nitrogen of the imido bond is suggested to possess an sp-hybridized character although the participation of an Sp(2)-hybridized character is indicated with the imido nitrogen derived from the triethanolaminate ligand.