Spherical calcium carbonate (CaCO3) is a potential component in many industrial fields such as high-grade papermaking, high-grade painting, environment, and pesticide. This paper describes a novel approach to synthesize spherical calcium carbonate (CaCO3) particles via passing CO2 bubbles into phosphogypsum salt leaching solution (CaSO4) in the presence of ammonia (NH3) at different temperatures. The influence of the initial solution pH and concentration of calcium ions on the polymorph and morphology of CaCO3 was studied. The physical characteristics of the precipitate were evaluated using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results showed that compared with different calcium sources the phase and morphology of CaCO3 synthesized by phosphogysum leaching solution had some regularity. The grain size of spherical CaCO3 became bigger, surface became smoother, and particle dispersion became better with the increase of calcium ion concentration. The content of vaterite increased and particle grain size changed a little with the increase of pH. The research results had important environmental significance for phosphogysum resource utilization and CO2 fixation.