Two new chitosan azacrown ethers bearing hydroxyl groups (CTS-DH and CTS-DO) were synthesized by the reaction of 3-hydroxyl-1,5-diaza-cycloheptane and 3-hydroxyl-1,5-diaza-cyclooctane with epoxy-activated chitosan. Their structures were characterized by elemental analysis, infrared spectra analysis, and X-ray diffraction analysis. The adsorption and selectivity properties of the hydroxyl azacrown ethers chitosan derivatives for Ag+, Cr3+, Cd2+, and Pb2+ were also investigated. The experimental results showed that the two novel chitosan azacrown ethers have good adsorption capacity for Ag+, and also showed that the grafted chitosan azacrown ethers have high selectivity for the adsorption of Ag+ in the presence of Pb2+ and Cd2+. The selectivity coefficients of CTS-DH and CTS-DO were KAg+/Pb2+ = 21, KAg+/Cd2+ = 42, KAg+/Pb2+ = 20.5, KAg+/Cd2+ = 41, respectively.