Abstract: The performance of the micro-X-ray fluorescence based on the slightly focusing polycapillary optics were investigated. While the chemical compositions of a piece of Pb-rich colored porcelain fired in Qing Dynasty were analyzed by micro-X-ray fluorescence. From the results, the processes of decorative technologies can be deduced as follows. A kind of pigments with high concentrations of Mn and Pb or with high concentrations of Fe and Pb was used to draw the profiles of designed paintings on the body of porcelain. Cu and its mixture with high concentration of Pb were filled in the desired positions. It is proved that polycapillary optics can play an important role in the analysis of the chemical characters and decorative technologies of pigments of colored porcelain.