Corydalis Rhizoma (Yanhuso), is a crucial antianalgesic Traditional Chinese Medicine in clinic. Its adulterants (Northeast Yanhusuo), which are also from Corydalis and distributed in Northeast area of China, are used instead of Corydalis Rhizoma in the local places with a long history. In this paper, we compared the chemical differences of Corydalis Rhizoma and its seven adulterants by HPLC-DAD-Q-TOF-MS associated with chemometric analysis. 48 alkaloids are identified from them, and 14 alkaloids are reported for the first time based on the Mass data. The classification of different species is verified through PLS-DA and Hierarchical Clustering Heatmap analysis based on 26 samples. We find that large discrimination existing in the categories and content of the alkaloids between different species. C.y. is similar with C.t., which mainly contains protoberberine, tetrahydroprotoberberine and protopine types of alkaloids. Six other Northeast Yanhusuo, including C.r., C.w., C.a. as well as its three formas, can be classified into one category, because they mainly contained benzophenanthridines and aprophines.