In this paper the development of a novel photoelectrocatalytic-enzymatic hybrid system for hydrogen production is presented. Together with hydrogen production in the cathode compartment of a photoelectrochemical cell, the destruction of the insecticide Imidacloprid, which acts as a model pollutant, will take place in the anodic compartment due to the photoelectrocatalytic effect. The photogenerated electrons in the Ti/TiO2 anode are transferred to the cathode where the hydrogenase enzyme derived from the algae Chlamydomonas reinhardtii, catalyzes the reduction of the H+ species to H-2. The optimization of both processes is being investigated for the purposes of this paper. 45% reduction in the organic carbon content of the Imidacloprid molecule was photoelectrocatalytically possible at the anode, while 21.3 mu mol H-2 per liter of the algae culture was simultaneously produced at the cathode over a period of 45 min. The production of the hydrogenase enzyme under photoheterotrophic and sulphur deprived conditions was confirmed by reverse transcription-polymerase chain reaction (RT-PCR). (C) 2012 Elsevier B.V. All rights reserved.