Perylene-sensitized mesoporous SnO2 films were used as electrodes for photoelectrochemical HBr splitting in aqueous solution. Upon AM 1.5 G illumination a 3-4 fold increase of the saturated photocurrent was observed when decreasing the pH of the aqueous solution from pH 3 to pH 0 (j max = 0.05 ± 0.01 mAcm-2 at pH 3 and 0.17 ± 0.02 mAcm-2 at pH 0, respectively). A detailed spectroscopic and electrochemical analysis of the hybrid material was carried out in order to address the impact of interfacial energetics on charge separation dynamics. UV/Vis spectroelectrochemical measurements showed that the energy of semiconductor states in such systems can be adjusted independently from the molecular levels by varying proton concentration. Photoelectrochemical measurements and ns-μs transient absorption spectroscopy reveal that pH-related changes of the interfacial energetics have only a minor impact on the charge injection rate. An increase of the proton concentration improves charge collection mainly by retarding recombination, which in the case of Br- oxidation is in critical competition with perylene regeneration. Control of the back recombination appears to be a key feature in heterogeneous molecular systems tasked to drive energetically demanding redox reactions.