A novel ergosterol conjunction-type alkaloid, hericirine (1), was isolated from the dried fruiting bodies of Hericium erinaceum. The overall framework of 1 was isolated, and combined with hericerin and ergosterol. Its structure was elucidated based on spectroscopic analysis using 1D and 2D NMR, IR, and HRESIMS techniques. We found that hericirine significantly inhibited protein expression of iNOS and COX-2 and reduced NO, PGE2, TNF-α, IL-6 and IL-1β production in RAW264.7 cells exposed to LPS.