A palladium-catalyzed distal C(sp2)-H chalcogenation of biphenyl amines is described. This protocol demonstrates scalability, excellent chemo- and regio-selectivity, and broad functional group tolerance, providing efficient access to valuable aryl chalcogenides. Notably, the chalcogenated biphenyl amines could be further transformed to 8-membered N, Se(S)-heterocycles through copper-catalyzed intramolecular C-N cyclization.