One challenge in the development of molecular photoswitches for solar energy storage is to increase the energy of the isomer formed upon irradiation. This work focuses on how to affect the relative stabilities of the isomers of the dihydroazulene/vinylheptafulvene (DHA/VHF) couple by combining the light-induced DHA to VHF conversion with the loss of aromaticity. We present a synthetic procedure for benzannulation of DHA at the C7-C8 bond, with the key steps being a stereoselective Diels-Alder cycloaddition followed by an oxidation. The optical properties and switching abilities of this compound are described in a combined theoretical and experimental study. Calculations support that benzannulation serves to increase the overall energy capacity of the photoswitch by stabilizing the DHA and destabilizing the VHF.