Daphenylline is a recently isolated Daphniphyllum alkaloid with an unprecedented novel hexacyclic scaffold. In this study, the synthesis of the fused all-carbon DEF tricyclic skeleton of daphenylline has been accomplished. Key steps of the reported sequence involve Evans asymmetric allylation, aldol condensation, Diels-Alder reaction, and oxidative aromatization reactions. The developed strategy might lead to the total synthesis of daphenylline. DEF-initely maybe: Synthesis of the fused all-carbon DEF tricyclic skeleton of daphenylline, a structurally novel Daphniphyllum alkaloid, has been accomplished based on a Diels-Alder/oxidative aromatization strategy. The finished approach, in combination with our previous research for the construction of the ABC ring system, may lead to the asymmetric total synthesis of daphenylline. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.