A procedure has been developed for the direct C sp2–H functionalization of phenanthridine with a 1H-benzotriazole residue in the presence of Selectfluor® to build up C sp2–N bond. The procedure makes it possible to synthesize 6-(1H-benzotriazol-1-yl)phenanthridine in one step using commercially available starting materials and reagents. The product is an important substrate for further chemical transformations.