The sulfatation of chitosan, by reaction with chlorosulfonic acid under controlled conditions, allowed increasing the pH range of chitosan solubility. The biopolymer was characterized using FTIR and <TEX>$^{13}C$</TEX>-NMR spectroscopy, elemental analysis and titration analysis and it was tested for mercury recovery by polymer enhanced ultrafiltration (PEUF). In slightly alkaline conditions (i.e., pH 8) mercury recovery was possible and at saturation of the polymer the molar ratio <TEX>$-NH_2$</TEX>/Hg(II) tended to 2.6. Polymer recycling was possible changing the pH to 2 and the polymer was reused for 3 cycles maintaining high metal recovery. The presence of chloride ions influences metal speciation and affinity for the polymer and "playing" with metal speciation allowed using the PEUF process for mercury separation from cadmium; at pH 11 the formation of hydroxo-complexes of Hg(II) limits it retention. Cake formation reveals the predominant controlling step for permeation flux.