A theoretical and experimental approach was applied to investigate phase relations in a system containing calcium carbonate and different ammonium phosphate solutions. Using laboratory experiments and thermodynamic modeling, this paper provides an insight into the formation of stable phase assemblages in the calcium carbonate and mono-, di-, triammonium phosphate aqueous system. Focus is placed on the morphological and mineralogical characterization and thermodynamic calculation of calcium phosphates precipitating due to the reaction between the calcium carbonate and ammonium phosphate solutions. Correlations between the formed stable calcium phosphate phases and the ammonium phosphate precursors are provided. Advantages and limitations of various analytical and modeling techniques used in this study such as geochemical equilibrium-based modeling, X-ray diffraction, scanning electron microscopy, and thermal analysis, are critically evaluated. Additionally, possible impacts of the ammonium phosphate solution type on the kinetics of phase transformations are discussed.