Vanadium (V) is an emerging contaminant in groundwater that can adversely affect human health. Although bioremediation has been shown effective, little is known on autotrophic V(V) bioreduction in the context of oligotrophic characteristics of groundwater. In this study, we demonstrate that efficient V(V) bioreductions can be coupled with bio-oxidation of elemental sulfur (S(0)) or zerovalent iron (Fe(0)), and the V(V) removal efficiencies reached 97.5 ± 1.2% and 86.6 ± 2.5% within 120 h using S(0) and Fe(0), respectively. V(IV) is the main reduction product and precipitates naturally in near-neutral conditions. Microbial community, functional gene, and metabolites analyses reveal that synthetic metabolisms among autotrophs and heterotrophs played major roles in V(V) reduction using S(0) and Fe(0). These results demonstrate a new approach for V(V) contaminated groundwater remediation.