Three-dimensional (3D) composites of hydroxyapatite, phosphorylated and/or nonphosphorylated chitosan and sulphonated methylsiloxane polymer (HA/P-CHI: CHI/ S-MSP) were prepared by solid-liquid phase separation and solvent sublimation method. The HA, P-CHI and S-MSP were synthesized by chemical continuous wet-calcination, phosphorylation reaction and hydrosilylation-sulphonation reactions, respectively. 3D composites were analyzed by scanning electron microscopy (SEM). Swelling ability, stability and formation of HA particles on the composites immersed in simulated body fluid (SBF) were analyzed. Osteoblasts showed high viability when cultured on composite scaffolds. 3D composites were not degraded after 8 weeks of subcutaneous implantation in rats.