There is an urgent need to develop more efficient microbial technologies suitable for vanadium (V) stressed environments. In this study, rice washing waste (RWW) was utilized as both the carbon and microbial sources immobilized together with sludge to treat V-containing wastewater. Continuous flow reactors were operated, and V(V) removal efficiencies (30 d) with polyvinyl alcohol (PVA) and chitosan as embedded carriers achieved 9.0% and 79.4%, respectively. A superior V(V) removal performance (91.45%) was achieved in the continuous flow reactors with chitosan-based immobilized materials (70 d). V was detected on the surface and within the material, and V(IV) was found, indicating that both adsorption and microbes were able to contribute to V(V) remediation. Increase in the fractions of some functional microbes were observed in response to V(V) stress (unclassified_f_Comamonadaceae, unclassified_f_Enterobacteriaceae) and ammonia stress (unclassified_f_Hungateiclostridiacea). RWW could serve as suitable carbon and microbial sources for long-term operation and enhance V(V) removal by immobilized together with sludge, thereby unveiling a new method for both food and V contaminants.