Poly(4-vinyl pyridine) decorated magnetic chitosan biopolymer (VMCP), as an absorbent and reductant, was prepared and used to remove hexavalent chromium (Cr(VI)) from aqueous solution. Compared with undecorated magnetic biopolymer, VMCP exhibited significantly improved removal performance under identical experimental conditions. The kinetics, isotherms, and thermodynamics of Cr(VI) adsorption onto VMCP were investigated. Results demonstrated that the maximum monolayer adsorption capacity of VMCP was 344.83 mg/g, which was considerably higher than most reported adsorbents. The mechanism for Cr(VI) removal was explored based on XPS and FTIR analyses. The main mechanisms were concluded to be Cr(VI) adsorption onto the positively charged VMCP surface and the reduction of Cr(VI) to Cr(III), followed by coordination between Cr(III) and N atoms. The easy regeneration, satisfactory reusability, and remarkable performance in column tests revealed the high potential of VMCP in treating Cr(VI)-contaminated water.