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Transferring abundant, inexpensive, and nontoxic carbon dioxide (CO2) into biodegradable polymers is one of the ideal ways to promote sustainable development. Although a great deal of preeminent researches has been reported in the last decade, including well-designed organometallic complexes, Lewis pairs, etc. The moisture- and air-sensitive nature of these extensively used catalysts preclude their use in industrial applications. Herein, we report a novel stable catalyst system of commercial zinc glutarate (ZnGA) with a supported metal for the synthesis of poly­(ester-b-carbonate). The special supported microstructure facilitates efficient polymerizations via a plausible heterometal coordination mechanism. Notably, the resulted biodegradable CO2-based copolymer showed strong tensile strength (>40 MPa), improved elongation (45% versus 7%), excellent transmittance, and low water vapor permeability (WVP) (1.7 × 10–11 g m–1 s–1 Pa–1). Moreover, the supported ZnGA catalyst is recyclable, and its simple and low-cost preparation process is compatible with the manufacturing and processing methods of the existing infrastructure.