Poly(ionic liquid)s (PILs) have gained widespread attention in recent years due to their excellent properties similar to both ionic liquids and polymers. However, their further applications are limited because abundant and flexible ions easily block nanopores in the PIL catalysts, thus blocking the active sites and ultimately leading to decreased catalytic activity. This work reports the synthesis of a PIL/graphene composite catalyst (iPOP-ZnTPy@GNFs) based on an in situ surface preparation strategy, which effectively controlled the particle size and dispersion state of ionic liquids. The iPOP-ZnTPy@GNFs exhibited a larger surface area and more exposed active sites, which intensified the catalytic activity in the CO2 cycloaddition reaction with propylene oxide with almost double the reaction rate as compared to that of iPOP-ZnTPy-2 at 100 °C and S/C = 1000. As expected, the iPOP-ZnTPy@GNF catalyst efficiently converted epoxides to cyclic carbonates at room temperature or atmospheric pressure, which can significantly reduce the process cost. In addition, iPOP-ZnTPy@GNFs exhibited excellent broad substrate scope, catalytic diversity, and remarkable reusability. The reaction mechanism of CO2 cycloaddition was studied via density functional theory calculations and was validated by experimental findings. This work provides a feasible method for improving the utilization of active sites in PILs as a highly robust catalyst for CO2 cycloaddition and can be further extended to other types of catalytic reactions in practical applications.