A cascade [4+3] annulation of o‐alkenyl bromoarenes and o‐bromoaniline derivatives was described. Various dibenzo[b,f]azepines with substitutions on the 10/11 position were obtained in 14–97% yields. The synthetic versatility of this protocol is highlighted by the preparation of a precursor of the drug molecule oxcarbazepine, a gram‐scale synthesis, and two product transformations. Unlike previous amination/Heck sequence, this cascade process is supposed to undergo a C(vinyl), C(aryl)‐palladacycle involved pathway.magnified image