The utilisation of Cu₂O photocathodes for photoelectrochemical water splitting requires their stabilisation due to photocorrosion in aqueous electrolytes. Ultrathin films of wide band gap semiconducting oxides deposited by atomic layer deposition (ALD) on top of cuprous oxide can perform the dual function of both facilitating charge extraction (through the creation of a p–n junction) and protecting the absorber material from the aqueous electrolyte, thereby suppressing corrosion in favor of hydrogen generation. The factors that determine the photocurrent performance as well as the stability of these photoelectrodes are examined. Specifically, the influence of ALD deposition temperature, electrolyte pH, electrolyte composition as well as post-deposition annealing treatments was studied. The successful development of protective overlayers must fulfil the dual requirements of favourable band alignments as well as chemical stability. At long time scales, the deactivation of the photocathodes proceeds through etching of the amorphous overlayer, accompanied by the loss of the platinum catalyst particles. Through the deposition of a semi-crystalline TiO₂ overlayer, 62% stability over 10 hours of testing has been demonstrated without re-platinization.