A new type of crosslinked chitosan was prepared using Dihydroxy azacrown ether as the crosslinking agent. Its structure was confirmed by elemental analysis, Fourier transform infrared (FTIR) spectra analysis, solid-state C-13 nuclear magnetic resonance (NMR) analysis, and X-ray diffraction analysis. Its static adsorption properties for Ag+, Cd2+, Hg2+, and Co2+ were studied. The experimental results showed that the Dihydroxy azacrown ether crosslinked chitosan has good adsorption capacities and high selectivity for adsorption of Ag+ with the coexistence of Hg2+ and Co2+. The selectivity coefficients of crosslinked chitosan are k(Ag)/Hg2+ = 5.47, k(Ag)/(2+)(Co) = 4.64, respectively.