One-step synthesis of alkylimidovanadium(V) triisopropoxides was demonstrated by the reaction of the corresponding alkylamines with [VO(Oi-Pr)(3)] in the presence of sodium hydride as a base under relatively mild conditions. From the reaction of 1-adamantylamine, [V(adN)(Oi-Pr)(3)] (ad: 1-adamantyl) was obtained. The chiral mononuclear compound having the amino moiety, [V(2-NH2C6H10N)(Oi-Pr)(3)], was synthesized from the reaction of (1R,2R)- or (1S,2S)-1,2-cyclohexanediamine with a stoichiometric amount of [VO(Oi-Pr)(3)]. In a solid state, [V(2-NH2C6H10N)(Oi-Pr)(3)] is present in a polymeric molecular arrangement through the intermoleculer coordination interaction of the amino group to the vanadium metal center. The use of trans-1,4-cyclohexanediamine resulted in the binuclear compound [{V(Oi-Pr)(3)}(2)(mu-trans-1,4-C6H10N2)], which forms an alkoxide-bridged polymeric structure. Crystallization of a 1:1 mixture of [{V(Oi-Pr)(3)}(2)(mu-trans-1,4-C6H10N2)] and trans-1,4-cyclohexanediamine gave the 1:1 complex having a polymeric arrangement based on the coordination of the amino groups.