Abstract We investigate the hydroxylation behaviour of mixed Co–Fe oxide nanoislands synthesized on a Au(111) surface under exposure to water vapour at vacuum conditions. The pure Co and Fe bilayer oxides both become hydroxylated by water exposure in vacuum conditions, albeit to a very different extent. It is however an open question how mixed oxides, exposing sites with a mixed coordination to Fe and Co, behave. By forming surface O species with a mixed Fe/Co coordination, we can investigate the nature of such sites. By means of scanning tunnelling microscopy and x-ray photoelectron spectroscopy, we characterize a series of Co–Fe oxides samples with different Fe contents at the atomic scale and observe a scaling of the hydroxylation degree with the amount of Fe inside the Co–Fe oxides. Our results indicate that the Fe dopants within the Co–Fe oxides have opposing effects on edge and basal plane sites modifying the maximum hydroxylation degree of pure cobalt oxide, perturbing the original binding sites of H, releasing the absorbed H or blocking the diffusion pathway of H.