Extensive efforts have been made in recent years to explore the photovoltaic and photoelectrochemical properties of fullerenes and their derivatives. The fabrication of fullerenes and their derivatives onto an electrode is a vital step for controlling the film morphology of the fullerene assemblies on the electrode surface in molecular scale, resulting in a large impact on the device performance. In this chapter, fullerene-modified electrodes for photoelectrochemical devices and solar cells are described in terms of their supramolecular self-organisation.