China is the largest planting country of asparagus (Asparagus officinalis L.) in the world. Caoxian, as the famous asparagus township in China, enjoys a reputation for producing asparagus with high yield and good quality, due to its unique geological characteristic. In this study, a method of reverse-phase ultraperformance liquid chromatography coupled with electrospray tandem mass spectrometry (RP-UPLC-ESI-MS/MS) was established for profiling metabolites from three segments (tip, mid, and base) of 'Caoxian white and green Asparagus'. A total of 114 metabolites were identified, among them, 43 were found for the first time in this vegetable. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) was applied to provide an overview of the metabolite profiles of Caoxian asparagus and to separate different segments of spears. The variables most decisive to discriminate among segments included 9 of the metabolites tentatively identified. This study will help to improve the protection of Caoxian asparagus geographical indication.