(Ammine)pentacarbonylvanadate(1-) reacts with various phosphines (L = Ph3P, Ph2P(CH2)nPPh2 (n = 0–2), (p-ClC6H4)3P, Me3P, HPh2P, F3P) to provide moderate to high yields of V(CO)5L−. Several of these materials have not been isolated previously and either are unavailable or are not easily prepared by other methods. Interestingly, the reaction of V(CO)6NH3 − with Ph4P2 in liquid ammonia provides high yields (70–75%) of previously unknown V(CO)5Ph2PNH2 −, isolated as the Et4N+ salt, while the same reaction conducted in THF provides lower yields (35–45%) of V(CO)5Ph4P2 −, isolated as the Ph4P+ and Ph4As+ salts. Proton-decoupled 31P NMR has been used to unambiguously show that V(CO)5Ph2P(CH2)nPPh2 − (n = 0–2) contain both ligated and unligated diphenylphosphino groups. Infrared and 1H NMR spectra of the products are also discussed with respect to proposed structures. This “labile ligand method” represents the best method presently available for the synthesis of V(CO)5PR3 − species.