The 1Δg O2 chemiluminescence expelled from thermodecomposition as well as 266 nm photolysis of an oxygen rich molecule, benzaldehyde hydrotrioxide, has been observed. The 1Δg O2 production through the excited-state proton (or hydrogen atom) transfer reaction is intriguing in terms of the mechanism. The probable explanation is the increase of the basicity for the carbonyl oxygen upon the π→π* transition, resulting in a great driving force for the proton (hydrogen atom) migration in the excited state. © 1990.