We report here a systematic study of the aromatic tetradehydro-Diels–Alder (Ar-TDDA) reaction to elucidate the factors that have significant effects on the distribution of linear and angular naphthalene products. Two factors were studied, that is, the nature of the linker and the steric bulk of the substituent of the enyne part. The structure of the linker has a tremendous effect on the product distribution. The effect of the steric bulk of the substituent is dependent on the linker structure, in other words, different preferences are observed for different linkers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim