Poly(propylene carbonate) (PPC) is a promising new sustainable polymer produced from carbon dioxide. PPC has inferior thermal stability which could be enhanced by synergistic blending with other polymers. Blends of PPC and the engineering thermoplastic polyoxymethylene are produced by melt compounding in various weight ratios. The compatibility of the blends is investigated using thermogravimetric analysis (TGA), differential scanning calorimetry, Fourier transform infrared spectroscopy (FTIR), density measurements, and scanning electron microscopy (SEM). TGA reveals that thermal stability of the blends increases dramatically in comparison to the neat PPC. A small shift in the glass transition temperature demonstrates the immiscibility of the blends but also indicates some compatibility, attributed to potential dipole–dipole interactions which are also corroborated with the FTIR results. A deviation of the rule of mixtures for density is found for some of the blends. SEM analysis of the blends shows two phase morphology; however, the interfacial adhesion appeared to be enhanced with increasing PPC content. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45823.