Text：A heptafluorobutyric acid-induced cross-dehydrogenative coupling reaction of arylamines with 1,2,4-triazines has been described. This metal-free protocol enables regioselective para-C-H hetarylation of diverse arylamines including well-known fluorophore scaffolds, such as triphenylamine, carbazole and phenothiazine, with easily accessible 1,2,4-triazines under mild conditions. This approach has promise potential for drug development and material design.