To address the urgent need for CO 2 utilization in climate change mitigation, this study presents a highly efficient Zn-gallate catalyzed polymer synthesis, directly incorporating CO 2 alongside lactide and propylene oxide. This versatile catalyst facilitates both one-step random and sequential polymerization strategies, providing access to a diverse range of CO 2 -polymers. By precisely controlling composition and architecture, we synthesized random terpolymers, incorporating CO 2 , with catalytic activities of 1.7–3.6 kg/g-cat and 9.4 − 36 wt% PLA, and block copolymers involving CO 2 with catalytic activities of 0.7–3.0 kg/g-cat and 15 − 76 wt% PLA. These precisely tailored CO 2 -polymers display their potential to replace fossil-fuel-derived plastics like LDPE. • High performance CO 2 -polymer synthesis, tailored composition and architecture. • Zn-gallate (8.8 kg/g-Zn): 20 times better than previous heterogeneous Zn catalysts. • CO 2 -polymers surpass LDPE: potential sustainable fossil-fuel plastic replacement.