A novel approach was tested for metallic silver recovery and power generation by using cathodic reduction in bioelectrochemical systems (BESs). In dual-chamber BESs (130 mL volume) with acetate as electron donor on anode, both Ag+ ions and Ag(I) thiosulfate complex in catholyte were reduced on cathode. The reduction rate of Ag+ was more rapid than the Ag(I) complex as expected by energetic analysis. X-ray diffraction (XRD) analysis indicated that electrodeposits on cathodes from both catholyte were metallic silver with >91% purity. The feasibility of metallic silver recovery with the BESs was confirmed using simulated photographic wastewater and up to 95% of Ag(I) removal was achieved. (C) 2012 Elsevier Ltd. All rights reserved.