Reaction of the Schiff base ligand (R)-2-(pyrrol-2-ylmethyleneamino)-2′-methoxy-6,6′-dimethyl-1,1′-biphenyl with tetrakis(dimethylamido)vanadium in toluene gives the mononuclear VIV title complex, [V(C2H6N)2(C20H19N2O)2]·C7H8, which was isolated as red crystals. The VIV cation is coordinated by two monoanionic bidentate Schiff base ligands and two N atoms of two dimethylamide anions in a VN6 distorted octahedral coordination geometry, in which two N atoms from the dimethylamide anions are placed in a cis-configuration.