Chromium dioxide dihydrogen and bis-dihydrogen complexes: (eta (2)-H-2)CrO2 and (eta (2)-H-2)(2)CrO2 have been prepared by co-condensation of the CrO2 molecules generated from laser ablation Of CrO3 with H-2 in excess argon at 11 K. Broad-band photolysis of the (eta (2)-H-2)CrO2 complex induced a photoisomerization to produce the HCrO(OH) molecule. In addition, laser-ablated Cr atoms reacted with H-2/O-2 mixtures to give primarily the CrO2 and (eta (2)-O-2)CrO2 molecules, while the (eta (2)-H-2)CrO2, (eta (2)-H-2)(2)CrO2 and HCrO(OH) molecules were also produced on annealing, and photolysis. The aforementioned species were unambiguously characterized by FTIR spectroscopy and density functional theoretical calculations.