The performance of heterojunction organic solar cells is critically dependent on the morphology of the donor and acceptor components in the active film. We report results of photovoltaic devices consisting of bilayers and bulk heterojunctions using poly(3-hexylthiophene) (P3HT) and Buckminsterfullerene C-60. White light power efficiencies of eta similar to 2.2% (bulk heterojunction) and 2.6% (bilayer) were measured after a thermal annealing step on completed devices. Optical and structural investigations on non-annealed bilayer thin films indicated a distinct porosity of the spin-coated polymer, which allows C-60 to penetrate the P3HT layer and to touch the anode. This resulted for these bilayer solar cells in the experimental observation that electrons were collected predominantly at the cathode after photo-excitation of P3HT, but predominantly at. the anode after C-60 excitation. A morphological model to explain the ambipolar charge collection phenomenon is proposed. (c) 2007 Elsevier B.V. All rights reserved.