Few studies have been published about large scale heterogeneous photocatalysis hydrogen generation with simultaneous removal of organic pollutants. The purpose of the present work was to study the simultaneous photocatalytic hydrogen production and organic pollutant removal under direct solar irradiation at pilot-plant scale. The experiments were performed in a Compound Parabolic Collector (CPC) at the Plataforma Solar de Almeria (PSA). The efficiencies of two different photocatalytic systems, one based on a nitrogen doped and platinized TiO2, and the other using a platinized CdS-ZnS composite were evaluated. Formic acid and glycerol were used as sacrificial electron donors. Also, experiments using real municipal wastewaters were carried out showing simultaneous hydrogen generation and partial water pollutant removal. The largest amounts of hydrogen were obtained with aqueous solutions of formic acid, although the experiments with real wastewater gave moderate amounts of hydrogen, pointing towards the possible future use of such waters for photocatalytic hydrogen generation. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.