A rhodium-catalyzed diastereoselective formal [5 + 2] annulation of indoles with cyclohexadienone-containing 1,6-enynes has been established via indole 2,3-difunctionalization, which provides rapid construction of indole-fused oxepines in good to excellent yields with a broad substrate scope. (https://doi.org/10.1021/acs.orglett.1c03106.)