Micro energy dispersive X-ray diffraction (EDXRD) analysis has importance application prospects in measuring the phase structure of small samples or sample micro-area. A novel method of micro EDXRD analysis using a self-development micro X-ray fluorescence spectrometer is proposed. The two-dimensional scan of a 4 mm×4 mm mico-area on the surface of a RMB-5-Jiao coin is made by a portable micro-beam X-ray fluorescence spectrometer based on polycapillary X-ray optics focusing (focal spot diameter is 190.7 μm). After the obtained data are processed, the mappings of Cu3Sn(0 8 3), CuO(2 0 2) and other crystal phases are presented. Simultaneously, the two-dimensional scan of an ore particle with diameter of about 1 mm is also made by a desktop micro-beam X-ray fluorescence spectrometer based on polycapillary X-ray optics focusing (focal spot diameter is 31 μm). The mappings of SiO2(3 2 9), Fe2O3(1 1 6) and other crystal phases are also presented. The results show that the micro-beam X-ray fluorescence spectrometer based on polycapillary X-ray optics focusing has a potential application in the micro energy dispersion X-ray diffraction analysis of small samples or micro-areas of samples.