A novel calcium-based magnetic biochar (Ca-MBC), made by pyrolyzing the mixture of rice straw, iron oxide (Fe3O4) and calcium carbonate (CaCO3), was developed in this study for remediation of co-pollution of arsenic and cadmium. Characteristics of the material showed that Fe3O4 and CaCO3 were adhered on the surface of biochar. The experiments on the effects of pH, adsorption kinetics and isotherm revealed that the Ca-MBC had a great ability to adsorb arsenic and cadmium within 0.5 h for cadmium and 12 h for arsenic with a maximum adsorption capacity of 6.34 and 10.07 mg g-1, respectively, and that the adsorption of both metals was pH-dependent from 2 to 12 with an optimal pH of pH 5. The mechanism of co-adsorption of Cd(II) and As(III) included both competitive and synergistic effects. The presence of As(III) enhanced Cd(II) adsorption by 3-16% while Cd(II) addition suppressed As(III) adsorption by 15-33%. The synergistic effects on As(III) and Cd(II) adsorption had resulted from the electrostatic interaction and the formation of type B ternary surface complexes. These new insights provide valuable information for the application of Ca-MBC as a potential adsorbent in treatment of water contaminated with As(III) and Cd(II).