Biochar (BC) obtained by the co-pyrolysis of municipal sewage sludge (MSS) and sunflower seed shells (SSS) was utilized to support nanoscale zero-valent iron particles (nZVI) for the synthesis of a composite material (nZVI-BC) for Cr(VI) removal from aqueous systems. A series of characterization methods confirmed successful immobilization of nZVI on the surface of biochar with no aggregation. Batch experiments showed that the initial pH, initial Cr(VI) concentration, and nZVI-BC dose all significantly affected the Cr(VI) removal using nZVI-BC. The kinetics for Cr(VI) removal via nZVI-BC could be better explained by the pseudo-second-order (PSO) adsorption model. Adsorption isotherms analysis demonstrated the superior Cr(VI) removal capability of nZVI-BC in comparison to bare nZVI and BC. nZVI-BC can be reused after the regeneration process by applying 0.1 M HSO and 0.1 M NaBH solutions. The reaction mechanism for Cr(VI) removal might involve its chemical reduction on the nZVI-BC surface. Overall, environmentally friendly nZVI-BC was highly efficient in Cr(VI) removal from aqueous systems.