Preferential adsorption of Cu contained in wastewaters is desirable as the Cu can then be reprocessed and reused more easily. In this study, biogenic elemental selenium nanoparticles (BioSeNPs) were assessed for their ability to preferentially adsorb Cu from an equimolar mixture containing Cu, Cd and Zn. Variations in metal to BioSeNPs ratios and initial metal solution pH improved the preferential adsorption capacity of BioSeNPs toward Cu, with the ratio of Cu adsorbed to combined Cd and Zn adsorbed varying from 2.3 to 6.6. More than 78% of the added Cu was adsorbed at an initial metal solution pH of 5.2 and metal to BioSeNPs ratio of 0.21 mg mg(-1) when the ratio of Cu adsorbed to the sum of Cd and Zn adsorbed was 23. Infrared spectroscopy revealed that the Cu, Cd and Zn were interacting with the hydroxyl and carboxyl surface functional groups of the BioSeNPs. The modeling of BioSeNPs' acid-base titration revealed the presence of high concentrations of carboxylic groups (C = 60.3 mol kg(-1)) with a pK(a) of 3.9, providing further evidence of their interaction with Cu. The adsorption of Cu resulted in a lower colloidal stability of the BioSeNPs as indicated by more than 99% retention of added BioSeNPs after adsorption of heavy metals and filtration. BioSeNPs showed a good preferential adsorption capacity toward Cu as compared to other adsorbent. This study provides a proof-of-concept for the preferential adsorption of Cu onto BioSeNPs which are present in the effluent of a bioreactor treating selenium oxyanions containing wastewater. (C) 2015 Elsevier B.V. All rights reserved.