Azulenopyridazines 6 were efficiently synthesized from ethyl 4-hydrazinylazulene-1-carboxylate (2) by p-toluenesulfonic acid-catalyzed imine formation and intramolecular cyclization followed by dehydrogenation using KOH/MeOH in one-pot operation. Thermal and photochemical reactions of azulenopyridazines 6 afforded 1-vinylazulenes 7 in good yields.