Although Cr(VI)-reducing and/or tolerant microorganisms have been investigated, there is no detailed information on the composition of the microbial community of the biocathode microbial fuel cell for Cr(VI) reduction. In this investigation, the bacterial diversity of a biocathode was analyzed using 454 pyrosequencing of the 16S rRNA gene. It was found that most bacteria belonged to phylum Proteobacteria (78.8%), Firmicutes (7.9%), Actinobacteria (6.6%) and Bacteroidetes (5.5%), commonly present in environments contaminated with Cr(VI). The dominance of the genus Pseudomonas (34.87%), followed by the genera Stenotrophomonas (5.8%), Shinella (4%), Papillibacter (3.96%), Brevundimonas (3.91%), Pseudochrobactrum (3.54%), Ochrobactrum (3.49%), Hydrogenophaga (2.88%), Rhodococcus (2.88%), Fluviicola (2.35%), and Alcaligenes (2.3%), was found. It is emphasized that some genera have not previously been associated with Cr(VI) reduction. This biocathode from waters contaminated with tannery effluents was able to remove Cr(VI) (97.83%) in the cathodic chamber. Additionally, through use of anaerobic sludge in the anodic chamber, the removal of 76.6% of organic matter (glucose) from synthetic waste water was achieved. In this study, an efficient biocathode for the reduction of Cr(VI) with future use in bioremediation, was characterized.