Communication: Polyaromatic hydrocarbons are model compounds for graphite and have interesting electronic and optoelectronic properties. The synthesis and preliminary characterization of hexaalkyl-substituted hexa-peri-hexabenzocoronenes (see Figure) are described. It is shown that they exhibit hexagonal columnar mesophases with remarkably large widths, e.g., 339 K for R = n-C12H25.