Hexavalent chromium in industrial wastewater is a major concern due to its extreme toxicity. This study investigates the removal of Cr(VI) using viable anaerobic granular biomass as a biosorbent. The effect of Cr(VI) concentration on biogas content and COD removal using batch studies indicated that the phase II (methanogenic-rich) culture was more sensitive than the phase I (acidogenic-rich) culture. Toxicity indices for both cultures using COD removal were developed based on linear-log interpolation. The median inhibition Cr(VI) concentration (IC50), for phase II cultures was found to be 263 mg/L, while that for phase I cultures was 309 mg/L. A sorption study was conducted on viable and non-viable (dried) phase I-rich biomass: both followed the Langmuir model. In addition, the biosorption capacity for metabolically inhibited biomass was 25% less indicating some level of cellular uptake associated with Cr(VI) removal. This study demonstrated the potential for a two-phase anaerobic treatment system for a Cr(Vl)-contaminated effluent. (c) 2008 Elsevier Ltd. All rights reserved.