A highly active zinc glutarate-double metal cyanide (DMC) composite catalyst (ZnGA/Zn-CrDMC) was designed for the carbon dioxide (CO₂) and propylene oxide (PO) copolymerization reaction. The composite catalyst was synthesized in a rheological phase reaction and characterized using Fourier transform infrared spectroscopy (FT-IR), powder X-ray diffraction (PXRD), and scanning electron microscopy (SEM). The synthesized composite catalysed the solvent free reactions of PO and CO₂ to afford biodegradable polypropylene carbonate (PPC) copolymer. ¹H NMR,¹³C NMR, FT-IR and ESI-TOF mass spectrometry measurements were employed to confirm the characteristics of the PPC produced. Under optimal reaction conditions (50 bar CO₂, 70 °C, 24 h), the ZnGA-Zn₃[Cr(CN)₆]₂ composite displayed higher catalytic activities in the copolymerization reactions than the individual catalysts. The ZnGA:Zn₃[Cr(CN)₆]₂ ratio of 15:1 gave PPC yield of 47.9 g polymer/g cat compared to ZnGA that produced 42.6 g polymer/ g cat in 24 h. In addition, the PPC produced from the composite catalyst displayed higher carbonate linkage content (Fc = 85.4 %) compared to the value of Fc = 33.9 %. obtained using the Zn₃[Cr(CN)₆]₂ catalyst. Similaly, the composite catalsyt produced PPC with molecular weight of 4200 g/mol and narrow polydispersity index of 2.2. The resultant PPC copolymer displayed good thermal stability, exhibiting a high degradation temperatures (TGA_-10%) of 229 °C and complete decomposition at 350 °C.