Currently, great interest is focused on developing auto-tandem catalytic reactions; a substrate is catalytically transferred through mechanistically distinct reactions without altering any reaction conditions. Here by incorporating a pyrrolidine moiety as a chiral organocatalyst and a polyoxometalate as an oxidation catalyst, a powerful approach is devised to achieve a tandem catalyst for the efficient conversion of CO₂ into value-added enantiomerically pure cyclic carbonates. The multi-catalytic sites are orderly distributed and spatially matched in the framework. The captured CO₂ molecules are synergistically fixed and activated by well-positioned pyrrolidine and amine groups, providing further compatibility with the terminal W=O activated epoxidation intermediate and driving the tandem catalytic process in a single workup stage and an asymmetric fashion. The structural simplicity of the building blocks and the use of inexpensive and readily available chemical reagents render this approach highly promising for the development of practical homochiral materials for CO₂ conversion.