Low cost semiconductor photocatalysts that can efficiently harvest solar energy to generate H 2 from water or biofuels will be critical to future hydrogen economies. In this study, low cost CuO/TiO 2 photocatalysts (CuO loadings 0–15 wt.%) were prepared, characterized and evaluated for H 2 production from ethanol–water mixtures (80 vol.% ethanol, 20 vol.% H 2 O) under UV excitation. TEM, XRF, EDAX, EPR, Raman, TGA, XPS and Cu L-edge NEXAFS data showed that at CuO loadings <5 wt.%, Cu(II) was highly dispersed over the TiO 2 support, possibly as a sub-monolayer CuO species. At higher loadings, CuO crystallites of diameter 1–2 nm were identified. The photocatalytic activity of CuO/TiO 2 photocatalysts was highly dependent on the CuO loading, with 1.25 wt.% CuO being optimal (H 2 production rate = 20.3 mmol g −1 h −1 ). Results suggest that sub-monolayer coverages of Cu(II) or CuO on TiO 2 are highly beneficial for H 2 generation from ethanol–water mixtures and support the development of a sustainable H 2 economy.