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/TiO 2 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 21.3μmol H 2 per liter of the algae culture was simultaneously produced at the cathode over a period of 45min. The production of the hydrogenase enzyme under photoheterotrophic and sulphur deprived conditions was confirmed by reverse transcription-polymerase chain reaction (RT-PCR).