<jats:title>Abstract</jats:title><jats:p>A new phytosphingosine‐type ceramide (<jats:bold>1</jats:bold>) was isolated along with nine other compounds—5α,8α‐epidioxy‐(22<jats:italic>E</jats:italic>,24<jats:italic>R</jats:italic>)‐ergosta‐6,22‐dien‐3β‐ol, 5α,8α‐epidioxy‐(24<jats:italic>S</jats:italic>)‐ergosta‐6‐en‐3β‐ol, (24<jats:italic>S</jats:italic>)‐ergosta‐<jats:italic>7</jats:italic>‐ene‐3β,5α,6β‐triol,(22<jats:italic>E</jats:italic>,24<jats:italic>R</jats:italic>)‐ergosta‐<jats:italic>7</jats:italic>, 22‐dien‐3β,5α,6β‐triol, inosine, adenine, <jats:sc>l</jats:sc>‐pyroglutamic acid, fumaric acid, and <jats:sc>d</jats:sc>‐allitol from the ethanol and chloroform/methanol extract of the fruiting bodies of the basidiomycete <jats:italic>Russula cyanoxanotha</jats:italic> (Schaeff.) Fr. The structure of (<jats:bold>1</jats:bold>) was established as (2<jats:italic>S</jats:italic>,3<jats:italic>S</jats:italic>,4<jats:italic>R</jats:italic>,2′<jats:italic>R</jats:italic>)‐2‐(2′‐hydroxytetracosanoylamino) octadecane‐1,3,4‐triol by means of spectroscopic and chemical methods.