Competition between charge recombination and the forward reactions required for water splitting limits the efficiency of metal-oxide photocatalysts. A key requirement for the photochemical oxidation of water on both nanostructured alpha-Fe2O3 and TiO2 is the generation of photoholes with lifetimes on the order of milliseconds to seconds. Here we use transient absorption spectroscopy to directly probe the long-lived holes on both nc-TiO2 and alpha-Fe2O3 in complete PEC cells, and we investigate the factors controlling this slow hole decay, which can be described as the rate-limiting step in water oxidation. In both cases this rate-limiting step is tentatively assigned to the hole transfer from the metal oxide to a surface-bound water species. We demonstrate that one reason for the slow hole transfer on alpha-Fe2O3 is the presence of a significant thermal barrier, the magnitude of which is found to be independent of the applied bias at the potentials examined. This is in contrast to nanocrystalline nc-TiO2, where no distinct thermal barrier to hole transfer is observed.