CASSCF and multireference MP2 calculations were carried out on thiophene-S-oxide (TO) and selenophene-Se-oxide (SeO), comparing the energies of the ground state to the first two electronically excited singlet and triplet states, using constrained optimizations and multiple fixed S-O or Se-O distances. For both molecules, one of the two triplet states smoothly dissociates to yield O((3)P) with little or no barrier. Single point calculations are consistent with the same phenomenon occurring for dibenzothiophene-S-oxide (DBTO). This provides an explanation for the inefficient unimolecular photochemical dissociation of O((3)P) from DBTO despite a phosphorescence energy below that of S-O dissociation, i.e., that S-O scission probably occurs from a spectroscopically unobserved triplet (T2) state.