We demonstrated that poly(acrylic acid) (PAA) was effective as an organic additive for the crystallization of calcium carbonate on single-phase calcite substrates with three different orientations, (10.0), (00.1), and (10.4) planes. Without PAA, oriented calcite crystals were formed with specific morphologies depending solely on the surface properties of their respective oriented substrates regardless of polarization treatment. Upon the addition of PAA, the precipitates on the oriented calcite crystals were flat island-shaped aggregates of prismatic calcite mesocrystals elongated along the c axis regardless of the surface properties of calcite substrates. These aggregates coalesced into continuous thin films with a thickness of 1.5–10.5 μm. The top surface of the mesocrystals was either triangular or three-point-star shape, regardless of polarization treatment. Their surfaces belonged to the (00.1) plane. The electric field generated by the polarized calcite substrates and the addition of PAA promoted the formation of continuous thin films of calcite and had a significant impact on the negatively charged surface of the calcite substrates. The electric field controlled the mass transport of the reactant ions and the amount of PAA–Ca2+ complexes adsorbed on the substrates. The matching between the PAA chain and ion arrangement on the oriented calcite substrates explained the preferential calcite crystallization.