A typical kind of silicate gangue — sodium pyroxenite (mainly containing NaFeSi2O6) in Baiyunebo iron ore is selected as the research object in this paper. The endothermic peak and the change of quality is definited by means of thermal analysis (DSC and TG) in the rising process. And then the samples are sintered at the peak temperatures. The main ingredients of sodium pyroxenite and the resultants are definited by means of X-ray diffraction analysis (XRD). The experiment ascertains the change law of physical and chemical properties of sodium pyroxenite such as thermal decomposition, softening, melting temperatures and the corresponding resultants, which provides basic data for exploring the formation mechanism of complex calcium ferrite (SFCA) in baogang special sintered ore.