In this paper we present a photoelectrocatalytic-enzymatic hybrid system for simultaneous hydrogen production and organic pollutants' reduction. The destruction of the antibiotic Chloramphenicol, which acts as a model pollutant, will take place in the anodic compartment, while simultaneously hydrogen is produced in the cathode compartment of an algae photoelectrochemical cell. The photogenerated electrons in a TiO2 anode are transferred to the cathode, where the hydrogenase enzymes derived from the algae Chlamydomonas Reinhardtii strain CC-124, catalyze the reduction of the H+ species to H-2. Parameters like the growing medium, detergent, electron relay and algae concentration have been optimized. Fifty percent reduction in the organic carbon content and almost complete destruction of the Chloramphenicol molecule is possible at the anode under photoelectrocatalytic conditions. Simultaneously in the cathode compartment and in the presence of the algae culture C Reinhardtii strain CC-124, 216 mu M H-2 is produced over a reaction time of 450 min, using 0.4 mM Triton X 100 for the cell membranes rapture and 0.05 mM Methyl Viologen (MV+2), which acts as an electron relay, in a Tris-acetate-phosphate (TAP) sulphur free medium. The expression of the hydrogenase enzymes under photoheterotrophic and sulphur deprived conditions has been confirmed by a reverse transcription-polymerase chain reaction (RT-PCR). (c) 2013 Elsevier B.V. All rights reserved.