In this Letter, we demonstrate that linear 2,3-diazanaphthalene (1), 2,3-diazaanthracene (2), and 2,3-diazatetracene (3) can be easily prepared through [4+2] cycloaddition reaction between 3,6-diphenyl-1,2,4,5-tetrazine as the diene and arynes as dienophiles, generated in situ from ortho-aminoarylcarboxylic acids. The physical properties and crystal packing of the prepared compounds 1–3 were fully investigated. In addition, the experimental data (e.g., band gap and band position) are further confirmed by theoretical studies.