Yellow colourants appear to have been rarely employed for tombs mural paintings in ancient China. The recently discovered mural paintings at Xi'an (dated to the Tang dynasty, 618–907 ce) offer fresh materials for characterization of yellow pigments, which can be potentially useful for filling the gap of the yellow pigments. Multi‐analytical approaches have been applied in this study, including chromaticity analysis, cross‐section, polarizing microscopy, Raman spectroscopy, scanning electron microscopy with energy‐dispersive spectrometry and X‐ray diffraction. The results show that the yellow pigment in three tombs is goethite (FeO[OH]), whereas in a late Tang tomb is vanadinite (Pb5[VO4]3Cl). Compared to geothite, vanadinite is even more rarely found in tomb mural painting and fewer reports have been mentioned, which led us to think about the accessibility of such pigment. Interestingly, Chinese craftspeople had a long history of interacting with the iron‐ or lead‐bearing minerals related to these yellow pigments, and there seem no critical technological barriers against extracting and using yellow by the Tang dynasty. The lack of yellow colourants in China tomb murals is more likely to be a cultural rather than technological choice.