Yellow pigment was extensively used on the mural paintings of a tomb of Tang Dynasty excavated in the southern suburbs of Xi'an City, which is relatively rare in other ancient Chinese tomb mural paintings. In this work, comprehensive analyses were conducted on the yellow pigment samples using micro-Raman spectroscopy and scanning electron microscopy energy dispersive spectroscopy (SEM-EDS) techniques. The Raman spectroscopy, micro-morphology and elemental composition of the yellow pigment in the mural were measured and the results were discussed. The colourant of the pigment was identified as vanadinite [Pb₅(VO₄)₃Cl], a natural mineral pigment which was rarely used in ancient Chinese paintings. The results were considered to be of essential importance for further restoration and conservation for the mural paintings. It is worth noting that the identification of yellow pigments by Raman spectra must be careful and combine with other analytical techniques to avoid misidentification.