We have investigated the structural and optical properties of P3OT and P3OT/fullerene thin films in view of their application as active layer in plastic solar cells. Films of these materials were prepared by spin coating from toluene solutions onto silicon substrates. Their optical properties were studied by spectroscopic ellipsometry, which provides the anisotropic dielectric function of the films. Moreover, structural properties were studied using X-ray diffraction. A close correlation between the results obtained by both methods could be found. Especially, the strong optical anisotropy of the films can be explained in terms of a preferable orientation of the polymer chains parallel to the substrate. The effect of the optical anisotropy on the performance of optoelectronic devices is discussed. (C) 2003 Elsevier B.V. All rights reserved.