Metal-organic frameworks (MOFs) have been hybridized with other functional materials, such as ionic liquids, covalent organic frameworks (COFs), and metallic nanoclusters, to fabricate composite materials. These composites possess the structural characteristics of their individual components and exhibit synergistic properties. In this work, we demonstrate the synthesis of core-shell structure UiO-66-NH2@PILs-x composite materials by encapsulating MOFs within ionic polymers (PILs) with varying thicknesses of PILs shell. These hybrid materials serve as bifunctional catalysts for the conversion of CO2 into cyclic carbonates under solvent- and additive-free conditions through a synergistic catalytic effect facilitating the conversion of CO2 into cyclic carbonates under solvent- and additive-free conditions through synergistic catalytic effect, exhibiting superior catalytic performance and excellent recyclability. This MOFs-based composite material provides a competitive approach for CO2 catalytic conversion.