Daphenylline is an alkaloid containing a tetra-substituted arene within a sterically compact hexacyclic scaffold. Here, the first total synthesis of daphenylline is described. A gold-catalysed 6-exo-dig cyclization reaction was exploited to construct the bridged 6,6-bicycle at an early stage, the aromatic moiety was forged through a photoinduced olefin isomerization/6π electrocyclization cascade followed by oxidative aromatization.