Princess Temple, located in the Wutai Mountain area of Shanxi Province, is an architectural relic of the Ming and Qing Dynasties that integrated a religious site with a place of folk entertainment. The wall paintings of Daxiong Hall were a relatively well-preserved Water-and-Land-Mural of the Ming dynasty. The research not only reveals the materials and artistry applied to wall paintings but also supplies first-hand data for selecting restoration materials and protecting the wall paintings in the future. The integration of analytical techniques applied includes optical microscopy (OM), Raman spectroscopy (RAM), Fourier Transform infrared spectroscopy (FTIR), laser particles size analyzer (LPSA), X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF), scanning electron microscopy with energy dispersive spectrometry (SEM-EDS) and pyrolysis-gas chromatography/mass spectrometry (PY-GC/MS). The results showed that the mural chose an adobe brick wall as the support structure, and the ground plaster layer was divided into a coarse mud layer and a fine mud layer, then coated with a white powder layer, and finally decorated with pigments on the surface. The wall-supported components and the base plaster layer are similar to those of the local soil. The overall particle size composition is powder in the majority, and the sand content of the fine mud layer is higher than that of the coarse mud layer. Furthermore, the coarse mud layer was mixed with wheat straw, and the fine mud layer was reinforced with fibrilla. In particular, infrared spectrum analysis determined Kaolin was determined as a white powder layer. The Raman spectroscopy analysis showed that the pigments used azurite, lead white, cinnabar, iron red, ferrite yellow, red lead, synthetic atacamite and botallackite. In addition, The black pigment was further determined as pine wood soot ink, according to the relative concentration of the main polycyclic aromatic hydrocarbons and the biomarkers of pine wood. At the same time, PY-GC/MS was applied to identify animal glue as an adhesive of pigments. The results could provide more original information for the study of the art history of Princess Temple and enrich the scientific understanding of the materials and workmanship of Water-and-Land-Murals in Shanxi in the Ming Dynasty.