Peniciside, a new fernene triterpenoid glycoside, was isolated from the EtOAc extract of the solid-state fermented rice culture of the fungus Penicillium sp. 169. Its structure was elucidated on the basis of spectroscopic analysis, and the absolute configuration was determined by X-ray crystallographic analysis and chemical methods. Peniciside is the first example of a fernene triterpenoid glycoside with two hydroxyls at C-19 and C-20.