Using simple and efficient celloidin membrane as basic template, and adding polyglycol reagent as assistant template, the calcium carbonate assembly sphere chains were synthesized. The length of chains was 6-8 µm, and the building block spheres were formed by nanoparticles with about 50 nm in diameter. All the products were characterized by transmission electron microscopy, X-ray powder diffraction, thermogravimetry analysis. The decomposition temperature increased by about 30 °C compared with the separate spheres, which may be caused by the bonding power of the spheres in chains. The products of calcium carbonate chains that kept in alcohol for 90d were found to have second-assembly to novel flower-like structures.