Effective activation of CO2 is a prerequisite for efficient utilization of CO2 in organic synthesis. Precisely controlling the interfacial events of solids shows potential for activation. Herein, defect-enriched CO2 with constructed interfacial frustrated Lewis pairs (FLPs, two adjacent Ce3+center dot center dot center dot O2-) effectively activates CO2 via the interactions between C/Lewis basic lattice O2- and the two O atoms in CO2/two adjacent Lewis acidic CO2 ions. Selective cyclic carbonate production from a catalytically tandem protocol of olefins and CO2 is used to demonstrate FLP-inspired CO2 activation.