In this study, the role of polymer in precipitation has been examined by studying the effect of poly(ethylene glycol) (PEG) on the formation of calcium carbonate particles. The CaCO3 particles were characterized by several techniques, such as FTIR, XRD, SEM, and particle size distribution analysis. In the absence of polymer, the mixing of reagents in an aqueous solution led to the formation of calcite crystals. Introduction of poly(ethylene glycol) molecules reduced the rate of crystallization process, and the effect was concentration dependent. In the presence of 0.05, 0.1, and 0.5 % of PEG, after 5 minutes of precipitation initiation, vaterite microspheres appeared in the system and which were transformed into calcite crystals after 24 hours. The calcium carbonate obtained with PEG was characterized by smaller sized particles in comparison with the ones without polymer.