The preparation and spectral properties of K3VO(CN)5, K4V(CN)7(H2O), K4V(CN)6, and K7V(CN)7 are described. The blue compound obtained when vanadium(III) salts are treated with saturated aqueous potassium cyanide has been isolated as K3·5V(CN)5·5(OH)0·5. The previously reported preparations of K2V(CN)6,K3V(CN)6 and K5V(CN)5NO,H2O are not confirmed.