Thin films of perylene on SiOx/Si(1 0 0) and SiO2/Si(1 0 0) substrates have been studied by X-ray photoelectron spectroscopy and atomic force microscopy. These investigations reveal that structure, morphology, and growth modes depend on the preparation parameters. By varying the deposition rate between 0.8 and 16 nm/min, a transition from island growth mode, with large and isolated crystallites, to a homogeneous film growth is observable. We can predict the growth of perylene on technologically relevant substrates: homogeneous smooth films at lower substrate temperature (below 200 K) and single grains, enough for single nanodevices, when the film is grown at higher substrate temperature. (C) 2009 Elsevier B.V. All rights reserved.