We examined effects of surface electric fields for the crystallization of calcite on polarized hydroxyapatite ceramics with and without polyacrylic acid (PAA) as soluble additive. Both on negatively and positively charged surfaces without PAA, the only precipitates were rhombohedra calcite crystals with the face of the {10.4} plane favorably oriented parallel to the surfaces. This oriented growth was explained by the nucleation theory in the presence of an external electric field. However, the addition of PAA drastically changed the situation of the calcite crystals, i.e., the crystallites were the hemispheric aggregates of calcite needles with a facetted rhombohedral {10.4} end face and flat island-shaped aggregates of ones with a rough (00.1) end face having a triangular shape. The calcite needles grew along the crystallographic [00.1] axis. This oriented growth was explained by epitaxy on the PAA-Ca2+ complexes adsorbing on the surfaces. The morphology of the PAA-Ca2+ complex assemblies adsorbing on the surfaces before the calcite nucleation was an important factor to control the structure of calcite aggregates formed following. This morphology was controlled by properties of the surface electric field and the spatial distribution of the negatively and positively charged sites in the PAA-Ca2+ complexes.