A new synthetic protocol that affords novel hexa-peri-hexabenzocoronene (HBC) derivatives with partial "zig/zag" periphery and dramatically different electronic properties has been developed, which represents an important step toward understanding structure-property relationships of graphitic materials. The scope of this methodology was broadened by application to a much larger polycyclic aromatic hydrocarbon (PAH) with a more extended "zig/zag" character.