An unprecedented one-pot C–H olefination/aza-Michael addition tandem process has been developed for the synthesis of pyrrolo[3,2,1-de]phenanthridines from 7-phenylindoles and alkenes using a [Cp*RhCl₂]₂/AgOAc/Me₄NOAc catalytic system. A relatively wide range of functional groups are tolerated, and a variety of pyrrolo[3,2,1-de]phenanthridines are obtained in good to excellent yields.