Abstract: The paper concerns in the structures, performances and characteristics and applications for archaeology of a new microX-ray fluorescence system based on rotating anode X-ray generator and polycapillary Xray optics. The polycapillary X-ray optics used here can focus the primary X-ray beam down to some tens of micrometers in diameters that allows for non-destructive and local analysis of sub-mm samples with minor/trace level sensitivity. In order to prove the potentials of this instrument used in archaeology, a piece of Chinese ancient blue and white porcelain produced in Ming Dynasty was analyzed. The results show that intensities of Mn-Kα, Co-Kα are variable in agree with the thick of blue glaze. The correlation analysis indicates the Mn and Co have the best correlations. So, the concentrations or ratios of Mn and Co are crucial to determine the provenance and identify from a fake one of Chinese ancient blue and white porcelain.