(Chemical Equation Presented) To generate dibenzotetrakisdehydro- and dibenzopentakisdehydroannulenes (- and -DBAs) having a highly deformed triyne moiety, [4.3.2]propellatriene-anneleted dehydro- and dehydroannulenes were prepared as their precursors. UV irradiation of the precursors resulted in the photochemical [2 + 2] cycloreversion to generate the strained - and DBAs, respectively. The DBA was not detected by 1H NMR spectroscopy, but it was intercepted as Diels-Alder adducts in solution, suggesting its intermediacy. Its spectroscopic characterization was successfully carried out by UV-vis spectroscopy in a 2-methyltetrahydrofuran (MTHF) glass matrix at 77 K and by FT-IR spectroscopy in an argon matrix at 20 K. On the other hand, the DBA was stable enough for observation by 1H and 13C NMR spectra in solution, though it was not isolated because of the low efficiency of the cycloreversion. The DBA was also characterized by interception as Diels-Alder adducts in solution and by UV-vis spectroscopy in a MTHF glass matrix at 77 K. The kinetic stabilities of the DBAs are compared with the related dehydrobenzoannulenes with respect to the topology of the π-systems. In addition, the tropicity of the DBA is discussed based on its experimental and theoretical 1H NMR chemical shifts.