The slow electron transfer rate is a bottleneck to the biological wastewater treatment. This study evaluated the concomitant biotransformation and nonenzymatic reduction of Cr(VI) mediated by sulfate reducing bacteria (SRB), especially for the reinforcing Cr(VI) reduction via accelerating the electron transfer by the in-situ biosynthesized iron sulfide nanoparticles (FeS NPs). The kinetic results showed that 10 mg/L Cr(VI) was completely removed by pre-cultured FeS NPs within 7 h with kCr(VI) of 2.6 × 10−4 s−1, one magnitude higher than that without FeS NPs. Despite its competing electron to postpone sulfate reduction, the reduction of Cr(VI) was markedly improved via nonenzymatic reactions by the sulfide, the product of sulfate reduction. In the reinforcing system (bio-FeS [email protected]), the bio-FeS NPs served as an electronic bypass conduit for CoQ could significantly amplify the electron flux, and switch the Cr(VI) reduction from intracellular space to extracellular environment, which had a great detoxification effect on the microorganisms, eventually markedly promoted electron transfer extracellularly and the reduction of Cr(VI). After the long-term acclimatization, Desulfovibrio became the dominant bacteria at the genus level and accounted for the relative abundance of 32%. This study provides an alternative to use biogenic FeS NPs for Cr(VI) remediation.