The novel azacrown ether chitosan derivatives (CCAE-I, CCAE-II) were prepared by reaction between crosslinked chitosan with epoxy-activated azacrown ethers. Their structures were confirmed by elemental FTIR spectra analysis and X-ray diffraction analysis. The adsorption and selectivity properties of the crosslinked chitosan azacrown ethers for Pb2+, Cu2+, Cr3+, Cd2+ and Hg2+ were also investigated. The experimental results showed that they have high adsorption capacity for Cu2+, Cd2+, and Hg2+. The adsorption capacity of CCAE-II is higher than CCAE-I for Cd2+ and Hg2+. The selectivity properties of CCAE are better than chitosan and crosslinked chitosan.