Chemically stable porous azacrown ether-crosslinked chitosan films were prepared by reacting varying molar amounts of N,N-diallyl-7,16-diaza-1,4,10,13-tetraoxa-dibenzo-18-crown-6 (molar equivalents ranging from 0, 0.125, 0.167, 0.25 and 0.5) with chitosan. Their chemical and structural properties were characterized by solid state-nuclear magnetic resonance (NMR), elemental, Fourier transform infrared (FTIR), microscopy, and X-ray analyses, as well as gel content. NMR and FTIR analyses of the reaction products suggested that new –CH2– crosslink bridges were produced between the amine groups of chitosan (Ch) and the allyl groups of the azacrown (DAC). The crosslinking chemistry between allyl and amine groups of the reactants was further evidenced with solution NMR studies on model compound of glucosamine with the azacrown. X-ray diffraction analysis of the Ch/azacrown films using wide angle X-ray scattering (WAXS),including synchrotron-WAXS, revealed that the crystalline arrangement of chitosan (Ch) was partially destroyed with increasing grafting of azacrown ether proportion on the Ch polymer chain. Solubility and gel content determination confirmed network formation with a gel content as high as 84–95 wt %. Microstructural analysis revealed microporous morphology with high surface area. The morphology and structure of the azacrown ether-crosslinked chitosan films could be tailored by stoichiometry of the reacting species.