The chemical fixation of CO 2 into epoxides for the synthesis of cyclic carbonates is an appealing solution to both reduce global CO 2 emission and produce fine chemicals, but it is still a prime challenge to develop a low-cost, earth-abundant, yet efficient solid catalyst. Herein, Fe 2 O 3 /NiFe 2 O 4 heterostructures are facilely constructed for the highly efficient cycloaddition of CO 2 with styrene oxide (SO) to produce styrene carbonate (SC). Both experimental findings and density functional theory (DFT) calculations substantiate the prominent electron transfer and charge redistribution within the heterointerfaces between the biphasic components, which induce a unique interfacial microenvironment that can facilitate the adsorption and activation of SO. This endows the biphasic catalyst with a substantially higher reactivity than the individual components. This study sheds new insights into the establishment of heterostructured catalysts consisting of transitional metal oxides for the high-efficiency production of SC from the cycloaddition of CO 2 with SO.