A copper-catalyzed radical cascade dehydrogenative cyclization of N-tosyl-8-ethynyl-1-naphthylamines under air is described herein for the synthesis of thioazafluoranthenes. The reaction proceeds smoothly with high efficiency and a broad reaction scope. The product is indeed a new fluorophore and its photophysical properties are also investigated. Based on the results, we are pleased to find that the Stokes shift of amino-linked thioazafluoranthenes in dilute tetrahydrofuran is determined to be 143 nm (4830 cm-1).