Photoelectrochemical hydrogen and oxygen production from water were demonstrated without external voltage using calcium iron oxide (p-type) and TiO2 (n-type) semiconductor electrodes. The calcium iron oxide electrode with the ratio Fe/Ca of 1.9, which consisted of two crystal phases (main phase: CaFe2O4, impurity phase: Ca2Fe2O5), showed the highest photocathodic current in 0.1 M NaOH aq. at potentials below +0.30V vs. Ag/AgCl under a 500W Xe lamp illumination, and TiO2 showed photo-anodic current in 0.1 M NaOH aq. at potentials over -0.78 V vs. Ag/AgCl. In the system where the two electrodes were connected under illumination, the open-circuit voltage was 1.09 V and the short-circuit current density was 550 mu A cm(-2). Hydrogen and oxygen were successfully generated from this present system without applying an external voltage. The ratio of hydrogen/oxygen evolved after 12-h reaction with both the electrodes short-circuited was around 3.7. This system is an ultimately artificial photosynthesis system where hydrogen and oxygen are generated separately under illumination. It is believed that this present system can form the basis of the future artificial photosynthesis system where hydrogen and oxygen are produced directly from water and sunlight. (C) 2012 Elsevier Ltd. All rights reserved.