We investigate thin poly(3-hexylthiophene-2,5-diyl)/[6,6]-phenyI C-61 butyric acid methyl ester (P3HT/PCBM) films, which are widely used as active layers in plastic solar cells. Their structural properties are studied by grazing-incidence X-ray diffraction (XRD). The size and the orientation of crystalline]P3HT nanodomains within the films are determined. PCBM crystallites are not detected in thin films by XRD. Upon annealing, the P3HT crystallinity increases, leading to an increase in the optical absorption and spectral photocurrent in the low-photon-energy region. As a consequence, the efficiency of P3HT/PCBM solar cells is significantly increased. A direct relation between efficiency and P3HT crystallinity is demonstrated.