The feasibility of simultaneous recovery of heavy metals from wastewater (e.g., acid mining and electroplating) and production of electricity is demonstrated in a novel photoelectrochemical cell (PEC). The photoanode of the cell bears a nanoparticulate titania (TiO2) film capped with the block copolymer [poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol)] hole scavenger, which consumed photogenerated holes, while the photogenerated electrons transferred to a copper cathode reducing dissolved metal ions and produced electricity. Dissolved silver Ag+, copper Cu2+, hexavalent chromium as dichromate Cr-2 O-7(2-) and lead Pb2+ ions in a mixture (0.2 mM each) were removed at different rates, according to their reduction potentials. Reduced Ag+, Cu2+ and Pb2+ ions produced metal deposits on the cathode electrode which were mechanically recovered, while Cr2O72- reduced to the less toxic Cr3+ in solution. The cell produced a current density J(sc) of 0.23 mA/cm(2), an open circuit voltage V-oc of 0.63 V and a maximum power density of 0.084 mW/cm(2). A satisfactory performance of this PEC for the treatment of lead-acid battery wastewater was observed. The cathodic reduction of heavy metals was limited by the rate of electron-hole generation at the photoanode. The PEC performance decreased by 30% after 9 consecutive runs, caused by the photoanode progressive degradation. (C) 2016 Elsevier B.V. All rights reserved.