AbstractSynthesis and photochemical generation of the octamethylene‐bridged 1,3‐cyclohexadiene and bicyclo[3.1.0]hexene derivatives1and2, which are to be classified as anti‐Bredt olefins, are reported.outOrientation of the octamethylene bridge at the sp3‐hybridized bridgehead atom of1generates strain effects whileinorientation of the bridge in2does not give rise to deformations of the bicyclo[3.1.0]hex‐2‐ene subunit. X‐ray analyses indicate a twisted double bond (12.2 and 15.0°) at the bridgehead atom of1and a deformation of the six‐membered ring from an ideal boat conformation. In contrast, the five‐membered ring of compound2is planar. The folding angle between the five‐ and the three‐membered ring is 111.8(2)°. The olefinic carbon atoms of1are