In this contribution, we reported a novel strategy to synthesize porous molecularly imprinted polymers (MIPs) of anticancer drug of doxorubicin hydrochloride (DOX) using reduction-cleavable hyperbranched polymers containing disulfide bonds (ds-HP-alkyne). The porous MIPs (MIP-DOX-HP) possess enhanced specific surface area and porosity by the incorporation of cleavable hyperbranched polymers from the copper(I)-catalyzed azide-alkyne click chemistry. In comparison to MIPs synthesized without using ds-HP-alkyne, MIP-DOX-HP exhibits more regular and open porous structures, which increase the loading and controlled release abilities of DOX anticancer drug. Under optimized pH condition, the total cumulative release amount of DOX at equilibrium is as high as 2134 and 1249 mu g for MIP-DOX-HP and MIP-DOX, respectively. The effective and robust strategy for synthesizing MIPs using cleavable hyperbranched polymers is helpful for extending applications of MIPs in drug delivery and target-activated release systems.