In polluted groundwater, surface water, and industrial sites, chromium is found as one of the most common heavy metals, and one of the 20 main pollutants in China, which poses a great threat to the ecological environment and human health. Combining biological and chemical materials to treat groundwater contaminated by heavy metals is a promising restoration technology. In this research, Klebsiella variicola H12 (abbreviated as K. variicola) was found to have Cr(VI) reduction ability. A high-efficiency Klebsiella variicola H12-carboxymethyl cellulose (abbreviated as CMC)-FeS@biochar system was established for Cr(VI) removal from aqueous solution. The Scanning Electron Microscope-Energy Dispersive Spectrometer (SEM-EDS), X-ray photoelectron spectroscopy (XPS) results indicated that CMC-FeS was successfully loaded onto the surface of biochar, and K. variicola H12 grew well in the presence of CMC-FeS@biochar with microbial biomass up to 4.8 × 108 cells mL-1. Cr(VI) removal rate of CMC-FeS@biochar system, K. variicola H12 system and K. variicola H12 + CMC-FeS@biochar system were 61.8%, 82.2% and 96.6% respectively. This study demonstrated K. variicola H12-CMC-FeS@biochar system have potential value for efficient removal of Cr(VI) from Cr(VI)-polluted groundwater.