The reactivity of water at Ag(111), Zn(0001) and Cu(111) surfaces studied by X-ray photoelectron and high resolution electron spectroscopies at low temperatures (80–295 K) is reviewed. Emphasis is given to the coadsorption approach in revealing mechanisms for oxygen–water reactions with comparisons made with previous studies and the models proposed for ammonia–oxygen reactions at metal surfaces. Transient dioxygen–water precursor states result in facile and extensive surface hydroxylation with implications for catalytic oxidation. The orientation of the hydroxyl states with respect to the surface normal are sensitive to the oxygen–water ratio and for high oxygen ratios (200:1) an unreactive oxide overlayer forms at Cu(111) and Zn(0001). The significance of weakly adsorbed complexes, dioxygen–water and carbon dioxide–water, is discussed and, provided they are not kinetically controlled, are models for reactions at high pressures and temperatures with insights to the mechanisms of “real” catalytic reactions. Although scanning tunnelling microscopy has revealed “complex and unpredictable” water structures at low temperatures at metal surfaces, their reactivity and surface dynamics have received less attention. Graphical Abstract