AbstractIntroductionLycorine, one of the most common alkaloids in Lycoris spp., is believed to possess pharmacological activity.ObjectiveTo discover and identify lycorine‐type alkaloids in the crude extracts of bulbs from six Lycoris spp. by ultra‐high‐performance liquid chromatography quadrupole time‐of‐flight mass spectrometry (UHPLC‐QTOF‐MS) detection.MethodologyA qualitative analytical method with a data mining strategy was utilised. Based on the fragmentation patterns of standards investigated in positive tandem mass spectrometry (MS/MS) mode, the fragmentation rules of lycorine‐type alkaloids were summarised. These types of alkaloids were additionally classified as different subtypes based on structural features and MS/MS fragmentation patterns, and the diagnostic ions for characterisation of different subtypes of alkaloids were designated.ResultsThirty‐seven lycorine type alkaloids, including 16 previously undescribed compounds, were efficiently screened out and tentatively identified from the crude extracts of six Lycoris spp. Lycoris sprengri may be a preferable species for studying or extracting lycorine‐type alkaloids because of elevated relative concentrations and highest diversity of alkaloids.ConclusionThe UHPLC‐QTOF‐MS and MS/MS data‐mining strategy proved useful for the detection and tentative identification of lycorine‐type alkaloids in bulbs of Lycoris spp. and could be extended to other Amaryllidaceae genera. The consequent profiling of the lycorine‐type alkaloids will be useful in the quality control of raw materials of Lycoris species and the exploration of superior species.