Organic electronics is one of the hottest and most exciting research topics today. However, its performance still lags behind that of inorganic-based electronics. This Progress Report demonstrates that by controlling the complexity of organic molecules at the molecular and at the supramolecular level as well as by choosing suitable processing techniques, the desired function for applications in electronics can be achieved. Our main focus is on polyphenylene-based nanomaterials, versatile organic molecules that allow access to novel intricate materials. We emphasize the molecular complexity as well as the supramolecular organization and the interfacing of novel organic materials as key guidelines.