Based on the basic principles of biomineralization, calcium carbonate (CaCO3) which has specific shapes can be synthesized by the biomimetic synthesis, using three-dimensional (3D) photonic crystals self-assembled by polystyrene spheres as the matrix (Ps film).The effects of variety and morphology of substrate on the crystal form and morphologies of CaCO3 were investigated. It was found that variety of substrates has great influence on the phase of calcium carbonate. On the Ps film, large amount of calcite and aragonite can be observed. SEM of the gold surface shows aragonite needles and vaterite. On the glass surface, large amount of vaterite can be observed. Ps films self-assembled by different diameters of polystyrene spheres have different morphologies and surface roughness, which have deep effects on the crystal form of calcium carbonate.This simple route might open opportunity to synthesis and the study of other novel inorganic materials.