Substantial relics are vital pieces of evidence for people to reconstruct historical details. By studying them, we can know ancient people’s lifestyles,production and the relationship with nature. X-ray spectroscopy (X-ray fluorescence spectrum and X-ray absorption fine structure spectrum) is an important non-destructive analysis method. It can be used to acquire some information such as elemental composition and structure of a complex containing specific ions to provide support for conservation and value perception of relics. Nowadays, these methods are widely used in a variety of substantial relics. This article briefly summarizes and introduces recent applications of X-ray spectroscopy in relic research. In general, X-ray fluorescence spectroscopy plays an important role in the provenance study of ancient ceramics, oil paintings and bronzes. Constructing database based on elemental composition acquired from the X-ray fluorescence spectrum and the effective use of X-ray absorption fine structure spectrum relics the study are the main difficulties andkey topics in the future application research.