The isoelectronic isomer of perylene, hereafter called as azuperylene, has been prepared. Electronic structure analysis reveals that the new isomer can be described as a union of two antiparallel azulenes in which the azulene-type aromatic character of the starting azulene is partially retained. Four 2,8-dialkoxy (i.e., ethoxy, n-butoxy, n-hexyloxy, and n-octyloxy) functionalized derivatives of the new isomer core have been prepared. The solid-state structures of the new compounds have been resolved showing exceptional herringbone π-π stacking ideal for charge transport. Organic field-effect transistors on sublimated substrates display an excellent hole transport mobility up to 1.03 cm V s that largely surpasses that of perylene and reveals the great potential for charge transport of this new class of nonbenzenoid compounds.