The intramolecular [2 + 2] photocycloaddition of three 4-(alk-4-enyl)coumarins and three 1-(alk-4-enoyl)-2,3-dihydropyridones was studied in the absence and in the presence of Lewis acids (irradiation wavelength λ = 366 nm). Spectral and kinetic data were collected for the respective parent compounds with a pent-4-enyl and a pent-4-enoyl chain. For the substrates with a methyl group in cis- or trans-position of the terminal alkene carbon atom (hex-4-enyl and hex-4-enoyl substitution), the stereochemical outcome of the [2 + 2] photocycloaddition was investigated. The mechanistic course of the uncatalyzed coumarin reactions was found to be a singlet pathway, whereas Lewis acid-catalyzed reactions proceeded with higher reaction rates in the triplet manifold. Contrary to that, the dihydropyridones underwent a fast triplet reaction in the absence of the Lewis acid. In the presence of a chiral Lewis acid the reactions slowed down but, due to the high extinction coefficient of the Lewis acid/dihydropyridone complexes at λ = 366 nm, still resulted in high enantioselectivity.