Photooxidation of Hantzsch 1,4-dihydropyridines (1,4-DHP,1a-1d) by direct irradiation (λ > 300 nm) under an oxygen atmosphere has been carefully examined in this work. Spectroscopic and electrochemical studies demonstrate that photoinduced singlet electron transfer from 1,4-DHP to molecular oxygen occurs. The generated superoxide radical anion (O2-·) is responsible for this typical photochemical oxidation. Photooxidation of Hantzsch 1,4-dihydropyridines (1,4-DHP, 1a-1d) by direct irradiation (λ> 300 nm) under an oxygen atmosphere has been carefully examined in this work. Spectroscopic and electrochemical studies demonstrate that photoinduced singlet electron transfer from 1,4-DHP to molecular oxygen occurs. The generated superoxide radical anion (O2- ·) is responsible for this typical photochemical oxidation.