An enantioselective total synthesis of pentacyclic proaporphine alkaloid (-)-misramine has been achieved. The synthetic route features a Pictet-Spengler cyclization to construct the fused B and C rings and a sequence of Baeyer-Villiger oxidation, Pinnick oxidation, and pinacol-type cyclization to install the alpha-hydroxy ketal moiety. The absolute configuration of the pentacyclic framework was elucidated by X-ray single-crystal analyses of (-)-11-demethoxymisramine.