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Recently, we reported enhanced H 2 evolution on TiO 2 -passivated GaAs. Based on density functional theory (DFT) calculations, this enhancement was attributed to Ti 3+ states, which bind reactant species and increase charge transfer across the semiconductor–liquid interface. Here, we provide a quantitative correlation between Ti 3+ density, as measured by X-ray photoemission spectroscopy (XPS) and photoluminescence (PL) spectroscopy, and photocatalytic performance, which substantiates the hypothesis put forth previously. In the photo- I – V characteristics reported here, passivating GaAs with TiO 2 produces a shift in the onset potential of +0.35 V at 1 mA/cm 2 and enhances the photocurrent by 32-fold over bare GaAs (at 0 V vs. RHE), resulting in a peak photoconversion efficiency of 1.5% under AM1.5 G illumination. We find that just 1 nm of TiO 2 produces the best conditions for photocatalysis. XPS spectra show that thinner TiO 2 films (1 nm) have a higher density of Ti 3+ states than thicker films (5 nm), which have lower photocatalytic performance. PL spectroscopy provides further evidence for these Ti 3+ surface states, which cause increased surface recombination. While it is apparent that the TiO 2 films cause strong electron–hole recombination, the benefit that they provide by providing catalytically active sites outweighs their detriment associated with charge recombination. No enhancement is observed for TiO 2 thicknesses above 10 nm, which are crystalline and, therefore, considerably more insulating than thinner amorphous TiO 2 films. [ABSTRACT FROM AUTHOR]