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The semiconducting materials used for photoelectrochemical (PEC) water splitting must withstand the corrosive nature of the aqueous electrolyte over long time scales in order to be a viable option for large scale solar energy conversion. Here we demonstrate that atomic layer deposited titanium dioxide (TiO2) overlayers on silicon-based photocathodes generate extremely stable electrodes. These electrodes can produce an onset potential of +0.510 V vs. RHE and a hydrogen evolution saturation current of 22 mA cm(-2) using the red part of the AM1.5 solar spectrum (lambda > 635 nm, 38.6 mW cm(-2)). A PEC chronoamperometry experiment was carried out for 2 weeks under constant illumination at +0.300 V vs. RHE with negligible degradation (