(R)-(+)-1-Phenylethoxide ligands were introduced into (4-methoxyphenylimido) vanadium(V) or (dimethylhydrazido) vanadium( V) compound to afford the chiral vanadium(V) compounds with the V=N bond, wherein a chiral dimeric structure was formed in a crystalline state through the mu-alkoxidobridging. Moreover, these chiral imido and hydrazido vanadium( V) compounds were demonstrated to dimerize by self-association at -80 degrees C even in a solution state.