Cobalt(III) and rhodium(III)-catalyzed regio- and chemoselective amidation of benzocyclobutenols has been realized using dioxazolone as the amidating reagent to afford three classes of C-N-coupled products via β-carbon elimination of the benzocyclobutenol. The Co(III)-catalyzed coupling initially afforded an isolable o-(N-acylamino)arylmethyl ketone, which could further cyclize to the corresponding indole derivatives under condition control. In contrast, efficient stepwise diamidation has been achieved under Rh(III) catalyst control. The chemoselectivities are jointly controlled by the catalyst and reactions conditions.