New azacrown ether chitosan derivatives (CTS-OC, CTS-NC) were synthesized by reaction of aryl mesocyclic diamine with the C6 hydroxyl group or C2 amino group in chitosan. Their structures were confirmed by elemental analysis, infrared spectra analysis, and X-ray diffraction analysis. The adsorption and selectivity properties of the aryl azacrown ethers chitosan derivatives for Hg2+, Cd2+, Pb2+, Ag+, and Cr3+ were also investigated. The experimental results showed that the two chitosan-azacrown ethers have good adsorption capacity for Pb2+, Cd2+, and Hg2+. The adsorption capacity of CTS-OC are higher than that of CTS-NC for Pb2+ and Cd2+. The chitosan-azacrown ethers have high selectivity for the adsorption of Pb2+ and Hg2+ with the coexistence of Cd2+. The selectivity properties of CTS-OC are better than those of CTS-NC.