Irradiation of 2-cyanobicyclo[2.2.1]hept-2-ene (2-cyanonorbornene, 4) in hexane, with the full arc of a mercury vapour lamp, gives the rearrangement products 1-cyanobicyclo[4.1.0]hept-2-ene 5 and 7-cyanotricyclo[4.1.0.03.7]heptane 6 in the ratio 20:1. These products were separated by preparative vpc. The structure of the major product 5 was determined by single crystal X-ray analysis. Reduction of 5 with lithium aluminum hydride gave the corresponding primary amine, which was converted to the p-bromobenzenesulfonamide 9, mp 150–151 °C, which gave single crystals from ethanol–water. The crystal and molecular structures are described. The minor product 6 was hydrogenated to give 7-cyanobicyclo[2.2. 1]heptane. Formation of 5 and 6 may involve concerted σ2s + π2s and σ2a + π2a processes respectively, which are photochemically allowed.