In this study, supercritical carbon dioxide (ScCO2), which is a sustainable and green solvent, was used as a reaction medium in the lipase‐catalyzed synthesis of anthrone‐functionalized benzylic amines for the first time. We synthesized the target compounds via a lipase‐catalyzed multicomponent cascade reaction of aldehydes, sulfonamides, and anthrones in ScCO2. The reaction can be accomplished in good‐to‐excellent yields (77 %–95 %) and can exhibit good functional group tolerance. In brief, the reaction was characterized by step economy, metal‐free conditions, environmentally friendly solvents, and biocatalysts.