Four new donor-acceptor triads (D-A-D) based on discotic and arylene mesogens have been synthesized by using Sonogashira coupling and cyclization reactions. This family of triads consists of two side-on pending triphenylene mesogens, acting as the electron-donating groups (D), laterally connected through short lipophilic spacers to a central perylenediimide (PI), benzo[ghi]perylenediimide (BI), or coronenediimide (CI) molecular unit, respectively, playing the role of the electron acceptor (A). All D-A-D triads self-organize to form a lamello-columnar oblique mesophase, with a highly segregated donor-acceptor (D-A) heterojunction organization, consequent to efficient molecular self-sorting. The structure consists in the regular alternation of two disrupted rows of triphenylene columns and a continuous row of diimine species. High-resolution STM images demonstrate that PI-TP2 forms stable 2D self-assembly nanostructures with some various degrees of regularity, whereas the other triads do not self-organize into ordered architectures. The electron-transport mobility of CI-TP2, measured by time-of-flight at 200 °C in the mesophase, is one order of magnitude higher than the hole mobility. By means of this specific molecular designing idea, we realized and demonstrated for the first time the so-called p-n heterojunction at the molecular level in which the electron-rich triphenylene columns act as the hole transient pathways, and the coronenediimide stacks form the electron-transport channels.