Laser-ablated vanadium atoms have been reacted with NO molecules during condensation in excess argon. Absorptions due to NVO (998.1, 906.4 cm(-1)), V-eta(1)-NO (1606.0 cm(1-)), V-eta(2)-NO (1075.7 cm(-1)) and V-(eta(2)-NO)(2) (1119.6,1153.8 cm(-1)) are observed and identified via isotopic substitution and DFT calculations. Higher nitrosyls are also formed on annealing. On the basis of the observed isotopic splitting, bands at 1614.5 and 1736.8 cm(-1) are assigned to antisymmetric and symmetric N-O vibrations of the C-2v dinitrosyl V(NO)(2), and 1715.1 and 1850.6 cm(-1) bands are assigned to the analogous vibrations of V(NO)(3) with G(3v) symmetry. The observation of (VO), (N2O) and (N-2), (VO2) complexes suggests that V atoms also react with (NO)(2) in these experiments.