Porous biodegradable microspheres were successfully obtained by an improvement single step and surfactant-free emulsion solvent evaporation method. The organic phase composed of PLA and dichloromethane was stirred in aqueous phase including Ca2+ ions to yield oil in water emulsion. During emulsification, stirring rate was increased so as to produce the W/O/W emulsion that results in microspheres with internal pores. The interface of internal water/oil was stable in W/O/W emulsion, which was explained that the bond between Ca2+ ions and carboxyl group of poly(lactic acid) would be stabilized the internal water/oil interface. Adding PO4 3- aqueous solution prompted to precipitate low crystallized hydroxyapatite on the external oil/water interface, and the precipitated hydroxyapatite would stabilizied microspheres formation. The resulting microspheres were approximately 100-500 µm with internal spherical pores of 10-200 µm in diameter. The porous biodegradable microspheres were expected to be utilized as injectable bone substitutes that allow bone ingrowth and bone regeneration.