The effects of polyacrylic acid (PAA) on the crystallization of carbonates were investigated, revealing a great influence of PAA on the shape, size and polymorph type of the carbonate crystals. Carbonate crystallization was performed through reaction crystallization in a single-jet system. The obtained crystals were measured and characterized by scanning electron microscopy and X-ray diffraction. In lithium carbonate, PAA especially influenced the growth phase, inhibited agglomeration and changed the crystal shape into high-aspect rods. In addition, the degree of the growth inhibition effect was molecular weight dependent and the inhibition effect was also different on each face. In calcium carbonate, an improvement of the monodispersity was observed with miniaturization, under particular conditions. Elongated calcite was found under a slow supersaturation rate. In addition, the molecular weight of PAA affected the polymorph selectivity. Therefore, PAA affected the crystallization phenomena of carbonates, and prospected crystals were obtained by changing the operation conditions.