An original strategy is proposed here to design chitosan-based ion-imprinted cryo-composites (II-CCs) with pre-organized recognition sites and tailored porous structure by combining ion-imprinting and ice-templating techniques. The cryo-composites showed a tube-like porous morphology with interconnected parallel micro-channels, the distance between the channel walls being around 15 μm. Both the entrapment of a natural zeolite and the presence of carboxylate groups, generated by partial hydrolysis of amide moieties, led to II-CCs with controlled swelling ratios (25–40 g/g, depending on pH) and enhanced overall chelating efficiency (260 mg Cu²⁺/g composite). To point out the importance of introducing Cu²⁺ recognition sites, sorption experiments using mixtures of Cu²⁺ and other competing ions (Co²⁺, Ni²⁺, Zn²⁺ or/and Pb²⁺) were also carried out. The higher values of selectivity coefficients obtained for the II-CCs compared to those of non-imprinted ones highlight the remarkable potential of our sorbents for decontamination of wastewaters and recycling of Cu²⁺ ions.