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CO 2 based-Poly(propylene carbonate phthalate) (PPC-P), a CO 2 -based polymer, is esteemed for its commendable mechanical properties, biodegradability and high transparency, positioning it as a promising material for sustainable packaging. However, its inherent brittleness and poor toughness significantly restrict its practical applications. This study addresses this limitation by incorporating ultra-high molecular weight poly(ethylene oxide) (UHMW-PEO) as an effective toughening agent. To overcome the melting processing challenges posed by the extremely high melt viscosity of UHMW-PEO, a novel hybrid methodology integrating solution blending, gradual dilution and melt blending is successfully implemented. The resulting blends exhibit excellent compatibility between PPC-P and UHMW-PEO because of the incorporation of entanglements introduced. Remarkably, the addition of a small amount of UHMW-PEO yields a toughened PPC-P material with an optimal balance of tensile strength, ductility and transparency. PPC-P/5%PEO formulation is selected for blown film extrusion, producing films that retain exceptional transparency (> 90%), robust barrier properties and a high tensile strength (∼ 22 MPa), while simultaneously exhibiting outstanding ductility (∼ 400% elongation at break) and impressive tear resistance (∼ 63 kN/m). These findings underscore the potential of this eco-friendly blend as a high-performance material for packaging articles. • Successfully addressed the inherent brittleness of the sustainable polymer PPC-P without sacrificing its valuable transparency, barrier properties, or tensile strength. • Developed a novel hybrid processing methodology (solution blending + gradual dilution + melt blending) to overcome the "un-processable" high melt viscosity of UHMW-PEO. • Achieved transformative toughening effects with only a small amount (5%) of UHMW-PEO, enhancing sustainability and cost-effectiveness. • Successfully produced blown films, demonstrating the formulation's feasibility for real-world packaging applications.