Laser-ablated group V metal atoms (V, Nb, Ta) were co-deposited with water molecules in excess argon. The V atoms reacted with water to form the inserted HVOH molecule spontaneously. The Nb atoms reacted with water to form the NbOH2 complex and the inserted HhTbOH molecule. Broad-band photolysis produced the H2VO and H2NbO molecules as well as the VO and NbO monoxides. For Ta + H2O reactions, neither TaOH2 nor HTaOH was observed, while the H2TaO molecule was produced on annealing, and the H-2 elimination process nias not observed on photolysis. The aforementioned species were identified via isotopic substitutions as well as density functional calculations. Qualitative analysis of the possible reaction paths leading to the observed products is proposed. The results have been compared with our earlier works concerning the Sc and roup IV metal atoms with water reactions in order to observe existent trends for the early transition metal atoms.