Rhodobacter sphaeroides O.U.001 can produce hydrogen under anaerobic conditions and illumination. The objective of this study was to investigate the performance of an 81 flat plate solar bioreactor operating in outdoor conditions. Different organic acids were used as carbon sources (malate, lactate and acetate) and olive mill waste water was used as a sole substrate source. The consumption and the production of the organic acids were determined by HPLC. The accumulation of by-products, such as poly-beta-hydroxybutyrate (PHB) and carotenoid, throughout the course of hydrogen production was determined. The hydrogen production rate was highest (0.01 l/l/h) when malate was the carbon source. Formate was observed as the fermentation end product. Acetate resulted in low hydrogen gas production and high PHB accumulation. When acetate was used as the carbon source, butyrate was produced as a result of fermentation. Promising amounts of PHB and caretenoid were accumulated during hydrogen production from diluted olive mill wastewater. (C) 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.