We have studied the self-assembly characteristics, the electronic structure, and the thermal stability of thin N,N′-bis(1-ethylpropyl) perylene-3,4,9,10-tetracarboxdiimide (EP-PTCDl) films grown on Ag (111) by a broad set of surface science analysis techniques. The deposition of single molecules to the formation of very thin films performed at room temperature under ultrahigh-vacuum (UHV) conditions was followed by atomic force microscopy (AFM), scanning tunneling microscopy (STM), ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy (XPS), and near edge X-ray absorption fine structure (NEXAFS), and was modeled by density functional theory (DFT) calculations. STM pictures show that substrate step edges are the stalling point for molecule adsorption, which is followed by formation of islands and eventually a monolayer. The monolayer is composed of large domains with ordered molecules with their perylene-3,4,9,10-tetracarboxdiimide (PTCDI) core lying almost parallel to the surface. For further exposure, multilayer stacked domains are formed. For thicker films molecular order could not be established. Upon heating it is found that the multilayer is stable up to 150°C where a rapid desorption takes place, followed by the dissociation of the molecules, leaving an ordered monolayer of presumably perylene core type molecules. © 2009 American Chemical Society.