Calcium deficient hydroxyapatite (CDHA) having an average particle size of 45 nm was synthesized by reverse emulsion method. It was converted to the respective biphasic calcium phosphate (BCP, 226 nm) and β-tricalcium phosphate (TCP, 450 nm) by calcination at 800 °C and 1000 °C, and the BCP consisted of 92% TCP and 8% CDHA. Subsequently, chitosan was mixed with calcium phosphates to prepare CDHA/chitosan, BCP/chitosan, and TCP/chitosan membranes. The initial moduli of the BCP/chitosan and TCP/chitosan membranes were about 1.9 times that of the pure chitosan membrane; and the elongations at break were almost 6 times. The CDHA/chitosan and BCP/chitosan could induce mineralization of apatite on the membranes by increasing 20.6 and 16.3 wt.%, respectively, after 24 days in the simulated body fluid. Moreover, the BCP/chitosan exhibited superior osteoblast cell attachment and proliferation than the other membranes. It has the potential to be used as the barrier membrane for guided bone regeneration.