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The counterfeit plant products, especially by using incorrect plant materials in pharmaceutical industry, have become a global problem. The plant materials belonging to closely related species but differing in medicinal properties are difficult to be identified. Here, a novel and generally applicable approach to identify the sources of plant materials was developed, which was based on the use of wooden-tip electrospray ionization mass spectrometry (wooden-tip ESI-MS) and multivariate statistical analysis of unidentified MS features (non-targeted). Using this approach, six officinal species of Fritillariae Cirrhosae Bulbus had been successfully differentiated. In addition, Fritillariae Pallidiflorae Bulbus, a common adulterant of Fritillariae Cirrhosae Bulbus, was also identified by using the strategy reported here. Compared with DNA phylogenetic trees, our approach provided finer resolution in distinguishing the closely …