(Amine)pentacarbonylvanadate(l−) reacts with various isocyanides, RNC (R = Me, c-Hx, t-Bu, Ph) to form [V(CO)5CNR]− in high yields (60–85%). These anions have been characterized by elemental analysis and infrared and 1H NMR spectra and are the first examples of (isocyanide)pentacarbonylvanadate ions. Treatment of Na[V(CO)6NH3] with NaCN in liquid ammonia provides, after cation exchange, up to 56% yields of [Et4N]2[V(CO)sCN]. The reactions of [V(CO)5NH3]- with n-BuNC and acetonitrile also provide V(CO)5L− species. On the basis of infrared spectra, these materials are formulated as [V(CO)5CN-n-Bu]− and V(CO)5(CH3CN)−, respectively. The latter product was isolated in 30% yield as a thermally unstable Ph4As+ salt.