Using neutron reflectivity, self-stratification in a model P3HT/PCBM blend is observed. The as-spun and solvent-annealed films show a depletion of PCBM near the top surface and enrichment of PCBM at the substrate (see figure). Depletion of PCBM at the cathode interface in a photovoltaic device could act as a barrier to efficient electron extraction. On thermal annealing, the PCBM depleted region is eliminated; an effect that partially explains the improvement of P3HT/PCBM devices on thermal annealing.