A novel C27N3-type pentacyclic Lycopodium alkaloid, lycoperine A (1) consisting of two octahydroquinoline rings and a piperidine ring, was isolated from the club moss Lycopodium hamiltonii. The structure and relative stereochemistry were elucidated on the basis of 2D NMR data and chemical transformation. Lycoperine A (1) exhibited an inhibitory activity against acetylcholinesterase.