Hydrogen production from water splitting into photoelectrochemical cells is a promising alternative for reducing the use of fossil fuels. Here, we synthesize by spray pyrolysis a porous ZnBi38O60/gamma-Bi2O3 film with a surface area of 744 m(2) g(-1) for use as a photocathode in water-splitting cells. The film of ZnBi38O60 with 3 wt% Bi2O3 has 2.3 eV bandgap energy and a conduction band energy of -2.14 V vs. RHE at pH 6.99, which is thermodynamically suitable for reducing H+ to H-2. Under illumination, the film produces a current density of -1.55 mA cm(-2) at 0 V vs. RHE with an onset potential of 0.84 V vs. RHE. HC-STH efficiency is 0.09% at 0.17 V vs. RHE and IPCE at 0 V vs. RHE is 3.8% at 480 nm. Under continuous operation, the ZnBi38O60/gamma-Bi2O3 film shows a stable photocurrent of -0.4 mA cm (-2) at 0 V. vs. RHE for 1800 s with 100% Faradaic efficiency. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.