The reactivity of a range of substituted divinylcyclopropanes towards the thermal Cope rearrangement has been examined. The effects of gem-dimethyl substitution on the cyclopropane, the alkene geometry, the relative stereochemistry of the cyclopropane and the steric and electronic effects of a range of functional groups were all examined, and the methods developed were used to synthesise a range of functionalised 1,4-cycloheptadienes in high yields.