Wastewater containing toxic hexavalent chromium (Cr(VI)) were treated with well-organized anaerobic granular sludge in this study. Results showed that the anaerobic granular sludge rapidly removed Cr(VI), and 2000 mu g.L-1 Cr(VI) was completely eliminated within 6 min, which was much faster than the reported duration of removal by reported artificial materials. Sucrose added as a carbon source acted as an initial electron donor to reduce Cr(VI) to Cr(III). This process was considered as the main mechanism of Cr(VI) removal. Methane production by anaerobic granular sludge was improved by the addition of Cr(VI) at a concentration lower than 500 mu g.L-1. Anaerobic granular sludge had a well-organized structure, which presented good resistance against toxic Cr(VI). Trichoccus accelerated the degradation of organic substances to generate acetates with a low Cr(VI) concentration, thereby enhancing methane production by acetotrophic methanogens.