The use of ochre is one of the signs of modern people’s behavior, in addition to stone artifacts that can reflect modern people’s cognitive ability and other deep-seated spirituals. In order to better understand the scientific information of ochre in archaeological sites from China regional, we used Raman, polarized light microscopy, and EDX to analyze the ochre in two archaeological sites of the Late Paleolithic period (Zhongshanshan site and Yahuai Cave site). The AMS dating results of the Zhongshan site show that the age was about 14 000 years ago, and the characteristics of the stone products of the two sites belong to the late Paleolithic period. Raman analysis showed that the peak values of all samples were consistent with ochre, the peak value was mainly 221 s, 290 s, 608 s and 662 m. Polarized light microscopic analysis showed that all samples were red ochre (oxide red). The sample is dark red under single polarizing light, with rounded edges. It is completely extinct under orthogonal slice light and has a large refractive index. The results showed that all ochre samples were mainly iron red, and no red pigments, such as cinnabar, were found. EDX analysis showed that all mineral samples contained Fe2O3. The content of Fe2O3 and SiO2 in chemical element composition is high, while the content of Al2O3, CaO, TiO2, TiO2 is low. Through the analysis of the SiO2 content of samples, it is shown that the SiO2 content is positively correlated with their hardness. Generally speaking, the main components of ochre found at the three sites were iron red pigments, and no other red pigments were found. This study is the first Raman and polarized microscopic analysis of the late Paleolithic ochre in China. The use of ochre by ancient humans in southern China can be further clearly dated to about 14 000 years ago (the Zhongshan site). The analysis of ochre materials from the two sites provides a basis for the scientific analysis data of late Paleolithic ochre in China and confirms the reliability of naked eye judgment of ochre materials. They were providing important potential value for the careful study and utilization of modern human behavior and ochre, providing important research materials and scientific data for the international study of ochre in China.