Submicrometer-sized, spherical vaterite particles were synthesized by solid-state reaction at room temperature in the presence of poly(acrylic acid)(PAA). The obtained products were characterized by XRD, IR and SEM. It was revealed that with increasing PAA amount, the crystal polymorph of CaCO 3 particles varied gradually from pure calcite through a mixture of calcite and vaterite to pure vaterite, and the particle size decreased generally. It was proposed that in solid-state reaction, PAA induced the formation of vaterite and the phase transformation from vaterite to calcite was prevented completely due to the absence of H 2O, resulting in the formation of pure vaterite particles.