Chemical reactions are generally assumed to proceed from reactants to products along the minimum energy path (MEP). However, straying from the MEP—roaming—has been recognized as an unconventional reaction mechanism and found to occur in both the ground and first excited states. Its existence in highly excited states is however not yet established. We report a dissociation channel to produce electronically excited fragments, S( ¹ D)+O ₂ (a ¹ Δ _g ), from SO ₂ photodissociation in highly excited states. The results revealed two dissociation pathways: One proceeds through the MEP to produce vibrationally colder O ₂ (a ¹ Δ _g ) and the other yields vibrationally hotter O ₂ (a ¹ Δ _g ) by means of a roaming pathway involving an intramolecular O abstraction during reorientation motion. Such roaming dynamics may well be the rule rather than the exception for molecular photodissociation through highly excited states.