Bioreduction of Cr(VI) is cost-effective and environmentally friendly, however, the slow bioreduction rate limits its application. In this study, the potential synergistic enhancement of Cr(VI) bioreduction by shewanella oneidensis MR-1 (S. oneidensis) with goethite and riboflavin (RF) was investigated. The results showed that the S. oneidensis reaction system reduce 29.2% of 20 mg/L Cr(VI) after 42 h reaction, while the S. oneidensis/goethite/RF reaction system increased the Cr(VI) reduction rate to 87.74%. RF as an efficient electron shuttle and Fe(II) from goethite bioreduction were identified as the crucial components in Cr(VI) reduction. XPS analysis showed that the final precipitates of Cr(VI) reduction were Cr(CH 3 C(O)CHC(O)CH 3 ) 3 and Cr 2 O 3 and adhered to the bacterial cell surface. In this process, the microbial surface functional groups such as hydroxyl and carboxyl groups participated in the adsorption and reduction of Cr(VI). Meanwhile, an increase in cytochrome c led to an increase in electron transfer system activity (ETSA), causing a significant enhancement in extracellular electron transfer efficiency. This study provides insight into the mechanism of Cr(VI) reduction in a complex environment where microorganisms, iron minerals and RF coexist, and the synergistic treatment method of Fe(III) minerals and RF has great potential application for Cr(VI) detoxification in aqueous environment.