A series of new unsymmetrical benzotrichalcogenophenes (BTCs) were synthesized by the Pd-N-heterocyclic carbene catalyzed intramolecular C3-arylation of furan, thiophene, selenophene and tellurophene units. This is the first time that a C3-direct arylation of selenophene and tellurophene moieties has ever been demonstrated.