Nondestructive analysis plays an important role in the studies of ancient artifacts. The present paper reports the chemical compositions and micro-area phases of 21 silicate artifacts samples analyzed by portable X-ray fluorescence spectrometer and laser Raman spectrometer. Based on the chemical compositions, these samples can be divided into PbO-BaO-SiO2, K2O-SiO2 glass systems, faience and PbO-BaO glassy faience which were discussed respectively, and preliminary investigation of colorants in different parts of some samples was also involved. By laser Raman spectroscopy, Chinese blue(BaCuSi4O10), Chinese purple(BaCuSi2O6) and Chinese dark blue(BaCu2Si2O7) were identified invasively in the blue pigment of some eye beads and circle beads, and then a variety of mineral phase including quartz, calcite, lead carbonate, burnt umber and terre verte were also analyzed successfully in the same way. According to the archaeological research results, the provenances of these samples were discussed briefly. PbO-BaO-SiO2 glass, K2O-SiO2 ear pendant and PbO-BaO glassy faience were made in China while the faience was suspected to be from the west. Those results illustrated the communications of culture and technologies among different regions of ancient China, and between ancient China and the western regions. The combination of portable X-ray fluorescence spectrometer and laser Raman spectrometer can provide chemical and phase information of relics, and has great advantages in scientific analysis of ancient artifacts, which supports future studies of archaeology.