Chitin, a polymer of 2-acetamido-2-D-glucose, and calcium phosphate composite was prepared by the process of phosphorylation of chitin substrate, Ca(OH)2 treatment and immersion in SBF solution. The C-6 chemical shift positions of 13C MAS NMR in the chitin fibres phosphorylated using urea and H3PO4 obviously indicate that phosphorylation takes place not in the C-1 but in the C-6 region. Chitin samples were phosphorylated using urea and H3PO4 and then soaked in saturated Ca(OH)2 solution at ambient temperature. This leads to the formation of thin coatings by particalhydrolysis of the PO4 functionalities, and stimulated growth of calcium phosphate coating on their surfaces after soaking in SBF solution was observed. The procedure can be applied to chitosan samples. This study demonstrates a useful method for creating faborable lacal conditions that lead to nucleation and growth of calcium phosphate over chitin or chitosan substrates.