The Five Northern Provinces'' Assembly Hall has the largest mural in Shaanxi Province. In order to get information on pigments used, paint layer samples were examined and analyzed by polarized light microscopy, microscopic examination on crosssections, xray fluorescence, xray diffraction, Raman spectroscopy and scanning electron microscopy with an energydispersive spectrometer (SEMEDS). The results show that only one red dyestuff was found in the main hall, other colorants are all inorganic. Red pigments are red lead, cinnabar and red ochre. Green ones are atacamite, malachite and botallackite. Blue pigments include Prussian blue, smalt and azurite. Yellow pigments are orpiment and yellow ochre. Brown pigments are mostly iron red ochre and PbO₂, an aging product of red lead. Black is flame carbons. White pigment is white lead, and lead white was also mixed with other colors for use. The research result suggested the study of the pigments used at the Five Northern Provinces'' Assembly Hall is important for understanding the mural painting technique used during the Qing Dynasty and architecture murals in the Shaanxi area.