Abstract
The mechanism of the photo-Smiles rearrangement involves formation of an intra-molecular radical ion-pair and a spiro-type Meisenheimer complex. The complete reaction pathways can be qualitatively described by the use of potential energy surfaces for the ground, the charge-transfer, and the locally-excited states. This can be regarded as an extention of the charge-transfer theory for aromatic substitution reactions developed by Nagakura to photochemical reactions.