Laser-ablated vanadium and titanium atoms were reacted with CO molecules during condensation in excess neon. The V(CO)(x) and Ti(CO)(x) (x = 1-6) molecules are formed during deposition or on annealing and photolysis. The V(CO)(x)(-), Ti(CO)(x)(-) (x = 1-6) anions and TiCO+ cation are also produced and identified on the basis of isotopic substitution and density functional calculations. Selective photolysis and CCl4 doping experiments strongly support the identification of the anions and cation.