Abstract One new fawcettimine‐type Lycopodium alkaloid , hupertimine F ( 1 ), together with five known ( 2 – 6 ) Lycopodium alkaloids were isolated from Huperzia goebelii . The structure of 1 was elucidated by 1D and 2D NMR spectra, HRESIMS, and X‐ray diffraction. Structurally, 1 represents the fourth example of Lycopodium alkaloids characterized by a 5/5/5/5/6 pentacyclic ring system with a 1‐ aza ‐7‐oxabicyclo[2.2.1]heptane moiety. These known compounds 2 , 3 , 5 , and 6 were isolated from H. goebelii for the first time. Compounds 1–6 were evaluated for acetylcholinesterase, butyrylcholinesterase and monoamine oxidase B inhibitory activities in vitro.