Grazing incidence X-ray scattering (GIXS) provides unique insights into the morphology of active materials and thin film layers used in organic photovoltaic devices. With grazing incidence wide angle X-ray scattering (GIWAXS) the molecular arrangement of the material is probed. GIWAXS is sensitive to the crystalline parts and allows for the determination of the crystal structure and the orientation of the crystalline regions with respect to the electrodes. With grazing incidence small angle X-ray scattering (GISAXS) the nano-scale structure inside the films is probed. As GISAXS is sensitive to length scales from nanometers to several hundred nanometers, all relevant length scales of organic solar cells are detectable. After an introduction to GISAXS and GIWAXS, selected examples for application of both techniques to active layer materials are reviewed. The particular focus is on conjugated polymers, such as poly(3-hexylthiophene) (P3HT).