Specific to calcium sulfoaluminate clinker and its hydration products, on the premise of confirming systemic error, Rietveld quantitative phases analysis was conducted with its quantitative results to compare to XRF, calorimetry and TG DTG results. The results show that systemic error of Rietveld quantitative phases analysis is around 1% for testing confirmed crystalline phases, error for calculating amorphous content decreases with amounts of inner standard increasing. In aspect of Rietveld quantitative phases analysis of calcium sulfoaluminate clinker, the optimal quantitative result can be obtained by employing both orthorhombic and cubic crystal file of C4A3＄, and the back stepping calculation of main elements is the most approximated to XRF results. In aspect of Rietveld quantitative phases analysis of hydration products, the reaction degree and AFt content, which are obtained by Rietveld method, are respectively well corresponded to calorimetry and TG DTG results.