Water adsorption and reaction on pure and Ni-modified CoOOH nanowires were investigated using ambient pressure photo emission spectroscopy (APPES). The unique capabilities of APPES enable us to observe water dissociation and monitor formation of surface species on pure and Ni-modified CoOOH under elevated pressures and temperatures for the first time. Over a large range of pressures (UHV to 1 Torr), water dissociates readily on the pure and Ni-modified CoOOH surfaces at 27 degrees C. With an increase in H2O pressure, a greater degree of surface hydroxylation was observed for all samples. At 1 Torr H2O, ratios of different oxygen species indicate a transformation of CoOOH to CoOxHy in pure and Ni-modified CoOOH. In temperature dependent studies, desorption of weakly bound water and surface dehydroxylation were observed with increasing temperature. Larger percentages of surface hydroxyl groups at higher temperatures were observed on Ni-modified CoOOH compared to pure CoOOH, which indicates an increased stability of surface hydroxyl groups on these Ni-modified surfaces.