There is still a significant challenge to realize the connection of CO2 capture anti utilization. Herein, we demonstrate an efficient and energy-saving system for tandem utilization of captured CO2 in order to produce cyclic carbonates with aqueous amine (BPEI10,000) as a CO2 adsorbent and a Cu(II) complex-intercalated porous organic framework as a heterogeneous catalyst. The porous organic polymer Bp-POF-Cu synthesized by the Schiff base reaction with a hierarchical microporous/mesoporous structure could efficiently catalyze cyclo-addition of CO2 with propylene oxide to afford a high turnover frequency of 1360 h(-1). With the in situ-released CO2 from BPEI10,000 solution as feedstock, up to 95% yield of cyclic carbonate was obtained over Bp-POF-Cu with epichlorohydrin as the substrate. The obtained results revealed that the CO2 desorption from amine solution and the catalytic reaction were successfully integrated, which demonstrated that the captured CO2 could be directly converted to cyclic carbonates in high yield through this heterogeneous catalytic system. Thus, we postulate that the tandem CO2 capture and cycloaddition reaction system presented here could offer an important method toward the implementation of the linking between CO2 capture and utilization.