The anaerobic antimonate [Sb(V)] reduction with a solid-state electrode serving as the sole electron donor was demonstrated by employing a bioelectrochemical system. The highest Sb(V) reduction efficiency was observed at the biocathode potential of -0.7 V versus standard hydrogen electrode using a cathode potential range from -0.5 V to -1.1 V. The scanning electron microscopy and energy dispersive X-ray spectroscopy indicated that both amorphous and crystallized Sb2O3 were formed as products of Sb(V) reduction. The irreversible recovery of bioelectrochemical Sb(V), when the cathode potential deviated from the optimal potential, was explained through the alteration in microbial communities, which was further elucidated by the next-generation sequencing of 16S rRNA gene amplicons. Chryseobacterium koreense and Stenotrophomonas nitritireducens were the dominant species of microbial consortia at Sb(V)-reducing biocathodes. This study revealed a novel option for bioremediation of Sb at underground contaminated sites, where the delivery of organic electron donors is limited or ineffective.