Display omitted •Ni/P25 TiO2 and Au/P25 TiO2 afford similar H2 production rates in alcohol-water mixtures.•Ni/P25 TiO2 outperforms Au/P25 TiO2 in methanol-water mixtures under UV excitation.•H2 production rates depend on the alcohol hole scavenger and alcohol concentration.•At 10 vol%, rates follow the order glycerol > ethylene glycol > methanol > ethanol.•At 40 vol%, rates follow the order methanol > ethylene glycol > glycerol > ethanol. This study systematically compares the performance of 0.5 wt% Ni/P25 TiO2 and 2 wt% Au/P25 TiO2 photocatalysts for H2 production in alcohol-water mixtures under UV excitation. HRTEM, XANES and EXAFS confirmed the presence of 5–8 nm Ni0 and Au0 nanoparticles on the surface of the photocatalysts. H2 production tests were conducted in various alcohol-water systems (0–100 vol%), using methanol, ethanol, ethylene glycol and glycerol. The Ni/P25 TiO2 and Au/P25 TiO2 photocatalysts demonstrated remarkably similar performance for hydrogen production in all the alcohol-water systems tested. At low alcohol concentrations (15 vol% or less), H2 production rates followed the order glycerol > ethylene glycol > methanol > ethanol, whilst at higher alcohol concentrations methanol (optimum 40 vol%) and ethanol (optimum 80–90 vol%) afforded the highest rates. Rates depended on the polarity and oxidation potential of the alcohol. Further, anatase-rutile heterojunctions in P25 TiO2 were found to greatly enhance H2 production.