The Shui-Lu wall paintings, a kind of religion-themed wall painting in North China, at Gucheng Temple is located on the walls of an early 16th century building—Sakyamuni Hall—of the temple. The theme of the paintings integrates three religions—Confucianism, Taoism and Buddhism—making the paintings an important case for the study of the history of Chinese painting art and the development of local religions in North China. However, the period of the paintings still remains controversial. There are two hypotheses:one tells that the paintings were finished in the same year of Sakyamuni Hall in 1507 (the 2nd year of the Zhengde period of the Ming Dynasty), which is referred to in a few publications; the other believes they were painted between the 1820s and 1840s (the Daoguang period of the Qing Dynasty), particularly earlier than 1849 (the 29th year of the Daoguang period) according to the records of the donors and related genealogies and inscriptions. We studied the craft and materials of the Shui-Lu wall paintings at Gucheng Temple. The result also contributes to the periodization of the paintings together with historical records. Based on onsite investigations, material analysis of the paintings was carried out using section microscopy, Raman spectrometry (Raman), scanning electron microscopy with energy dispersive spectrometry (SEM-EDS), X-ray diffraction (XRD) and infrared spectrometry (IR). As a result of the analysis, the structures and material compositions of the paintings were clarified. The structural layers of the paintings from inside to outside are core support, coarse plaster layer, fine plaster layer, white ground layer, paint layer and embossed painting and gilding craft. The difference is that the painting on the north wall consists of sketch layer, sticker layer (paper) and paint layer in turn outwards on the white ground layer. The coarse plaster is dominated by loess and wheat-straw, and the fine plaster is mainly composed of clay, pebble (0.5~2 mm) and animal fibers—usually, small pebbles are rarely seen in the fine plaster of painting. The pigments used on the paintings are mostly minerals. The red and orange ones are cinnabar, the pink one is mixed with red lead and cinnabar, the black one is carbon black, and the blue one is Prussian blue. The green pigment is botallackite, with a small amount of chalcocite, which was rarely found on wall paintings in China. The gold foil used in the embossed painting and gilding craft is Au-Ag-Pb alloy, with Au accounting for 75.19%, namely Dachijin. Using IR, the material of the sticker layer in the painting on the north wall was identified as paper, which was made with the addition of ceramic clay; the pigments used were consistent with those on other walls. The presence of the sticker layer beneath the paint layer of wall paintings is an extremely rare phenomenon, and few related reports are available. Considering that Prussian blue was introduced and exported into China during 1760s to 1770s (the mid and late Qianlong period of the Qing Dynasty), and Yuxian County, where Gucheng Temple is located, was a local commercial hub from mid-17th century, it is believed that the paintings were finished between 1760s and 1849 (from the mid and late Qianlong period to the 29th year of the Daoguang period). In this study, material analysis was innovatively applied to the periodization of wall paintings. It not only describes a scientific methodology to estimate the period of East-Asian wall paintings, but also contributes to the understanding of the Shui-Lu wall paintings of Gucheng Temple for its conservation and restoration. The outcomes of this study provide reference about local wall paintings’ craft and materials in Yuxian County, and also help to comprehend the social and technical development in pre-modern North China.