The thermal tetradehydro-Diels-Alder (TDDA) reaction for the synthesis of polysubstituted aromatic compounds remains underestimated probably due to the harsh conditions and multiproduct results. Herein, a mild intramolecular TDDA reaction of aryldiyne compounds is presented with linear naphthalenes only, exhibiting good functional group tolerance. The reaction is easy to operate and amenable to multigram-scale synthesis. From the preliminary work, it was found that the mild conditions may be the key to the completely linear product in the reactions.