Semiconducting small molecules capable of self-organizing into well-defined nanostructures have a great potential in organic electronics. In this article we review hydrogen-bond- directed supramolecular organization of barbiturated oligothiophenes and the application of the resulting one-dimensional nanostructures to solution processable bulk heterojunction organic photovoltaic cells. Through this article we illustrate that through a proper molecular design we can utilize directional hydrogen bonding units as a potent tool to organize pi-conjugated molecules into 1D nanostructures optoelectronically active at the device level.