A simple and efficient route for one-pot synthesis of high-molecular-weight aliphatic polycarbonates (APCs) by directly melt transesterification of diphenyl carbonate (DPC) with aliphatic diols at equimolar amounts was developed. Zn(OAc) 2 was found to be the best catalyst for this reaction among the screened transition metal acetates. The effects of reaction conditions on M w and yield of the poly(1,4-butylene carbonate) (PBC) were investigated, where the highest M w of 156200 g/mol with yield of 83 % was obtained under suitable reaction conditions. In addition, based on the results of thermogravimetric and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscope (SEM) and fourier transform infrared spectroscopy (FT-IR), a plausible reaction mechanism over Zn(OAc) 2 was proposed for APCs synthesis.