Rationale Norpimarane diterpenes possess plentiful bioactivities and are widely distributed in herbs, such as Flickingeria fimbriata. Rapid characterization of these natural products in complicated plant extracts is of great importance, and electrospray ionization tandem mass spectrometry is a powerful tool for chemical constituent profiling. However, limited researches on their fragmentation mechanisms seriously hinder identification via mass spectrometry. Methods Three norpimarane diterpenes isolated from F. fimbriata via multiple types of column chromatography served as reference compounds, and collision‐induced dissociation experiments were performed on them with a series of variable collision energies. Plausible fragmentation pathways were proposed based on product ions. To further validate the fragmentation mechanisms, the proton affinity and product ion energy were simulated by density functional theory at the B3LYP/6‐31+G(d, p) level. Results Three main cleavage reactions induced skeleton breakage and resulted in characteristic ions, methyl (CH3‐20) migration, hydrogen arrangement and Retro‐Diels–Alder reaction, among which methyl migration was firstly proposed for pimarane diterpenes. A series of common diagnostic ions were identified, such as m/z 133.1012, 121.1012, 119.0805 and 107.0855. Additionally, the constructed fragmentation mechanisms were successfully applied for fragment ion rationalization of previously reported isopimarane diterpenes. Conclusions Fragmentation mechanisms of norpimarane diterpenes have been uncovered. Carbocation located at the C ring tends to result in methyl (CH3‐20) migration which has been rarely reported before. This characteristic dissociation reaction allows multiple diagnostic ions to be rationalized and aids in rationalizing fragmentation patterns of other diterpenes. The uncovered mechanisms also shed light on rapid identification of norpimarane diterpenes.