A novel sterically congested Lycopodium alkaloid named lycopalhine A (1) that possesses a fused hexacyclic (5/5/5/6/6/6) ring system comprising a 5,9-diaza-tricyclo[6.2.1.04,9]undecane moiety and a tricyclo[5.2.1.04,8]decane moiety was isolated from Palhinhaea cernua L. The structure and absolute configuration were determined by spectroscopic and computational methods. © 2012 The Royal Society of Chemistry.