Four Tang Dynasty tombs with mural paintings have been excavated in southern suburbs of Xi’an. These tombs date from the early to the late Tang Dynasty. In order to identify the composition and discuss the history of application of yellow pigments used for these mural paintings, polarizing microscopy, Raman spectrometry, scanning electron microscopy-energy dispersive spectrometry (SEM-EDS) and X-ray diffraction (XRD) analysis were carried out. Results of the analysis show that yellow pigments used for the three mural paintings from the early to the middle Tang Dynasty are goethite, while that for a late Tang Dynasty mural painting is vanadinite, which is the first case of its use in the late Tang Dynasty ever found (before, uses of vanadinite were found only in mural paintings of a Western Han Dynasty tomb and the tomb of Han Xiu of the flourishing Tang period). The finding of vanadinite as a yellow pigment could be an important supplement to evidence for studying the history of application of vanadinite in mural paintings in Xi’an. In addition, according to a survey of relevant literature, the pigments in this paper were supposed to have been obtained from local sources.