The red and green colored porcelain is an important overglaze colored porcelain in the history of Chinese ceramics. It is significant to analyze the chemical composition and phase structure of the colored pigments to study the process of fired technologies. However, the traditional X-ray diffractometer with a 1 mm×10 mm line source is not easy to measure the porcelain sample of uneven surface and unevenly distributed color material. The capillary-focused X-ray diffractometer has a point X-ray beam to irradiate the sample. The capillary X-ray lens has a magnification of up to 3 orders of magnitude to the energy of Cu-Kα and has a low divergence of the X-ray beam. Therefore, it can measure the sample with a diameter of 100 micrometers and the conventional X-ray diffraction analysis of a sample with diameter of 3 mm, which is very suitable for the non-destructive analysis of the mineral structure of ancient ceramic samples. This article reports the results of the chemical composition and phase structure of the white glaze and red and green-colored pigments in the Qing Dynasty unearthed in Jingdezhen, Jiangxi province by the capillary focused microbeam X-ray fluorescence spectrometer, and the capillary focused X-ray diffraction spectrometer developed by our laboratory. It carried out the two-dimensional scanning analysis of the distribution of multi-element and mineral phases in the interest region (2 mm×2 mm) of the red and green colored porcelain. The results show that at first, Cu is the main coloring element of green colored pigments and the concentration of Cu in green colored pigments is 0.02%. Moreover, parts of Cu exist in the form of the Pb₈Cu(Si₂O₇)₃ crystal phase. Secondly, Fe is the main coloring element of red-colored pigments, and the contractions of Fe in red-colored pigments is 1.63%, and parts of Fe exist in the form of the Fe₂O₃ crystal phase; Thirdly, the concentrations of Pb in green and red-colored pigments is 41.49% and 6.29%, respectively. The main function of Pb is to lower the melting point of the colored pigments, and parts of the Pb combined with Cu and Si during the firing process at 700~800 ℃ to exist in the form of Pb₈Cu(Si₂O₇)₃ crystal phase. From the element 2D mapping and crystal phase mapping, it is obvious that the crystal phase of the coloring elements Cu and Fe in the colored pigments is inconsistent with the element distribution of Cu and Fe. It indicates that the Cu and Fe mineral crystal phases in the raw materials may disappear during the firing process, and the Fe₂O₃ crystal phases have been left or generated during the process of firing or cooling. The mullite crystal phase in the white glaze indicates that the white glaze fired at a high temperature. However, the formation temperature of the Pb₈Cu(Si₂O₇)₃ crystal phase is only about 750 ℃, which can further explain that the red and green colored pigments were fired at low temperatures. In general, the capillary-focused microbeam X-ray fluorescence spectrometer and the capillary-focused microbeam X-ray diffraction specrometer could have important application prospects in cultural relics’ scientific and technological research.