Angelicae Sinensis Radix, Danggui in Chinese, is an important traditional Chinese medicine derived from the roots ofAngelica sinensis (Oliv.) Diels. HPLC-ESI-MSn was applied to analyze the chemical constituents in the methanol extract ofDanggui. A total of 24 compounds were identified or tentatively characterized based on their UV and mass spectra, containing11 phenolic compounds, 12 phthalides and 1 amino acid. Three dicaffeoylquinic acids, 5-feruoylquinic acid and ferulic acidhexoside were detected in A. sinensis for the first time. According to Chinese medicine theories, the three parts of Danggui(Guitou, Guishen, Guiwei) have different therapeutic effects and their substantial evidence has not been clearly elucidatedyet. In the present study, the chemical compositions of different parts of Danggui were investigated by using the establishedHPLC method. The result indicated that the content of tryptophan was getting lower and the contents of low polarity constituentslike phthalides trended to get higher from Guitou to Guiwei. This might partly explain the therapeutic effects of differentparts of Danggui.