Zinc glutarates were synthesized from zinc oxides with varying purities via different stirring routes. The particle size and structure of these zinc glutarates were determined by wide-angle X-ray diffraction, transmission electron microscopy, and the laser particle size analyzer technique. The results demonstrated that the crystallinity and crystalline perfectness of zinc glutarate are the crucial factors that affect the catalytic activity for the copolymerization of carbon dioxide (CO2) and propylene oxide (PO). Additionally, the catalyst with a small particle size dramatically increased the yield of the copolymerization between CO2 and PO. High-molecular-weight and regular molecular structure poly(propylene carbonate)s (PPC)s were obtained from CO2 and PO with the synthesized zinc glutarates. Very high catalytic activity of 160.4 g polymer/g catalyst was afforded. The NMR technique revealed that the PPC copolymer exhibits an exact alternating copolymer structure. The relationships between the crystallinity and the particle size of catalyst with the catalytic activity are correlated and discussed.