A novel chitin-based biosorbent (QCP) was synthesized by cross-linking quaternized chitin and branched polyethylenimine with the aid of epichlorohydrin for efficient removal of Cr(VI) from water. Because it possessed both quaternary ammonium groups and amino groups as well as the hierarchical pore structure, QCP presented a maximum adsorption capacity of 387.7 mg/g according to the Langmuir isotherm at 25 degrees C. The biosorption of QCP achieved the equilibrium within 40 min and followed the pseudo-second-order kinetic model. QCP worked well even in the solution with high pH and high content of competing anions and, it exhibited an excellent reusability. The main Cr(VI) uptake mechanism was confirmed to be electrostatic attractions between Cr(VI) anions and quaternary ammonium groups as well as the protonated amino groups, and followed by partial reduction of Cr(VI) to Cr(III) by amines and hydroxyls. This work may provide a potential for Cr(VI) removal by chitin-based biosorbents.