A strategy for assembling biaryls linked through a medium‐sized ring is herein presented. π‐Complexation of fluoroarenes to chromium tricarbonyl activates the molecule towards both C−H activation and nucleophilic aromatic substitution without covalently altering the molecular connectivity of the arene. The construction of bridged biaryl molecules with 6–10‐membered core rings is achieved through a one‐pot C−H arylation/nucleophilic aromatic substitution sequence. The methodology is applicable to the synthesis of heterocyclic as well as fully carbocyclic rings
