Dimesitylboron-functionalized stilbene derivatives have been found to undergo an unusual regioselective photoisomerization upon irradiation at 365 nm. Using NMR to follow the photoreaction, the structures of key reaction intermediates and the final products were established. This photoisomerization occurs in four steps: trans-cis isomerization, Diels-Alder reaction, di-π-methane rearrangement, and ring opening with [1,3]-H migration. This results in the formation of a rare structure with three fused five-membered rings and a six-membered one.