Synthetic concepts toward the synthesis of large, not-fully benzenoid polycyclic aromatic hydrocarbons (PAHs), decorated with phase-forming and solubilizing n-dodecyl chains, are presented based on the intramolecular cyclodehydrogenation reaction of suitable oligophenylene precursors. The formal addition of successive C2 units into the armchair bays of the parent hexa-peri-hexabenzocoronene extends the aromatic system and leads to PAHs with a partial zigzag periphery. This variation of the nature of the periphery, symmetry, size, and shape has a distinct impact upon the electronic properties and the organization into columnar superstructures. Both computational and experimental UV/vis spectra, which are in good agreement, emphasize the dependence of the characteristic bands alpha, p, and beta upon the overall size and symmetry of the PAHs. While the number and the substitution patterns of attached n-dodecyl chains do not influence the electronic properties, the thermal behavior and supramolecular organization are strongly influenced, which has been elucidated with differential scanning calorimetry (DSC) and 2D wide-angle X-ray diffractometry (2D-WAXS) on mechanically aligned samples. This study provides valuable insight into the future design of semiconducting materials based on extended PAHs.