Thin epitaxial and polycrystalline CuInS2 (CIS) films were grown on single crystalline Si(111) and Mo-coated Si substrates, respectively, by means of molecular beam epitaxy from elemental sources. Photoluminescence (PL) measurements were performed to investigate the optical properties of both, epitaxial and polycrystalline CIS films. Epitaxial CIS samples show defect related transitions only and the PL spectra are dominated by broad luminescence peaks of deep levels, while excitonic transitions are completely absent. This contrasts sharply with the PL of the polycrystalline films, which is dominated by excitonic luminescence. Contributions due to shallow defects are observed with a small intensity only. However, luminescence peaks of defects with electronic levels deep in the band gap are not present at all. This includes the broad PL lines around 1.2 or 1.3 eV which are typical for polycrystalline CIS solar-cell material. X-ray diffraction and selected area electron diffraction measurements were employed in order to study the crystal structure. The epitaxial CIS films show a coexistence of the metastable CuAu-type (CA) ordering with the ground-state chalcopyrite (CH) structure, while the polycrystalline layers crystallize exclusively in the ground-state CH ordering. Hence, the coexistence of the metastable CA ordering and the ground-state CH structure in the epitaxial films is accompanied by a high density of electrically active intrinsic defects with levels deep in the band gap. (C) 2008 Elsevier B.V. All rights reserved.