<jats:title>Abstract</jats:title><jats:p>A new C<jats:sub>18</jats:sub>‐ceramide congener named pecipamide (<jats:bold>1</jats:bold>), together with the known ergosta‐4,6,8(14),22‐tetraen‐3‐one (<jats:bold>2</jats:bold>), was isolated from the solid fermentations of the basidiomycetous fungus <jats:italic>Polyporus picipes</jats:italic>. The structure of the new metabolite was established as (2′<jats:italic>R</jats:italic>,2<jats:italic>S</jats:italic>,3<jats:italic>R</jats:italic>)‐<jats:italic>N</jats:italic>‐2′‐hydroxyheptadecanoyl‐2‐amino‐octadecane‐1,3‐diol on the basis of spectroscopic data, including 1D‐ and 2D‐ nuclear magnetic resonance spectroscopy (NMR) experiments, as well as by means of mass spectrometric measurements (MS).