Abstract Chitosan is a novel glucosamine biopolymer derived from the shells of marine organisms. This biopolymer is very attractive for heavy metal ion separations from wastewater because it is selective for toxic transition metal ions over less toxic alkali or alkane earth metal ions. Highly porous, 3-mm chitosan beads were prepared by an aqueous phase-inversion technique for casting gel beads followed by freeze drying. In the attempt to simultaneously improve material properties and adsorption capacity, chitosan was chemically modified by 1) homogeneous acylation of amine groups with nonanoyl chloride before bead casting, and 2) heterogeneous crosslinking of linear chitosan chains with the bifunctional reagent glutaric dialdehyde (GA) after bead casting but before freeze drying. The random addition of C8 hydrocarbon side chains to about 7% of the amine groups on uncrosslinked chitosan beads via N-acylation improved the saturation adsorption capacity from 169 to 216 mg Cd2+/g-bead at saturation (pH 6.5, ...