This paper addresses the origin of the decrease in the external electrical bias required for water photoelectrolysis with hematite photoanodes, observed following surface treatments of such electrodes. We consider two alternative surface modifications: a cobalt oxo/hydroxo-based (CoOx) overlayer, reported previously to function as an efficient water oxidation electrocatalyst, and a Ga2O3 overlayer, reported to passivate hematite surface states. Transient absorption studies of these composite electrodes under applied bias showed that the cathodic shift of the photocurrent onset observed after each of the surface modifications is accompanied by a similar cathodic shift of the appearance of long-lived hematite photoholes, due to a retardation of electron/hole recombination. The origin of the slower electron/hole recombination is assigned primarily to enhanced electron depletion in the Fe2O3 for a given applied bias.