Calcium phosphate precursory powders containing Na and Mg have been prepared by the citric acid sol-gel combustion method. The elements of Na and Mg were introduced from component of CaO- P2O5-Na2 O-MgO. The effect of sintering additives on the phase composition was characterized by XRD. The effect of sintering additives on sintering of materials was also characterized by linear shrinkage, TEM and SEM. Finally the microstructure of porous calcium phosphate ceramic was determined by SEM.