The abovementioned examples underscore the required combined computational and experimental evidence for the assignment of a homoaromatic electronic structure. However, structural information is difficult to access, since neutral homoaromatics are often transient species and not crystalline, hampering the identification of bond length equalization as one of the key criteria for homoaromaticity. We herein present the synthesis of a neutral class of homoaromatic hydrocarbons, homoannulenes 6, and discuss its homoaromaticity, supported by experimental data (chemical shifts from NMR spectroscopy and bond length comparison from X-ray structure elucidation) and calculations. We further show that compounds 6 act as a structurally novel photochemical switch through an unprecedented reversible photo-induced [1,11] sigmatropic rearrangement forming a novel neutral 10 homoaromatic.