The ZnS-ZnO heterostructured photocatalysts are synthesized by thermal treatments of the ZnS materials at various thermal processing temperatures (150 degrees C - 550 degrees C) with controlling O-2 partial pressures (7.8 kPa - 33.8 kPa). The ZnS-ZnO composite structure shows much higher photocatalytic hydrogen production than those from the ZnS and ZnO pure substances. This phenomenon is mainly caused by effective charge separation between the photoexcited electrons and holes. The thermal oxidation of ZnS materials proceeds at temperatures higher than 500 degrees C. In addition to the thermal processing temperature, O-2 partial pressure is also chosen for an experimental variable in order to control the atomic composition minutely. The ZnS-ZnO photocatalyst composite fabricated at 500 degrees C under 16.9 kPa of O-2 partial pressure shows the highest hydrogen production rate of 494.8 mu mol g(-1) h(-1) under 1 sun irradiation condition, and it is 37 times higher than that (13.5 mu mol g(-1) h(-1)) from the ZnS pure substance. At this optimized production rate, the Zn/S/O atomic compositions are measured as 45.9/46.9/7.2 (XPS) and 53.3/42.1/4.6 (ICP-AES), respectively. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.