The growth of the polycyclic aromatic hydrocarbon perylene on (110) oriented copper substrates has been studied by means of x-ray photoelectron spectroscopy, near-edge x-ray absorption spectroscopy, and atomic force microscopy. In the monolayer regime, the molecules are orientated with their molecular plane parallel to the substrate, whereas they adopt a tilted arrangement in multilayer films. For multilayers with thicknesses exceeding 10 nm, the molecules grow in a bulk-like structure with their long axes orientated upright to the substrate surface.