The Cu(In,Ga)Se-2/Mo and the Mo/glass interfaces in high efficiency thin film solar cells have been investigated by surface-sensitive photoelectron spectroscopy and bulk-sensitive X-ray emission spectroscopy. The interfaces were accessed by a suitable lift-off technique. Our experiments show a strong Se diffusion from the absorber into the Mo film, suggesting the formation of a MoSe2 layer in the surface-near region of the back contact. In addition, we find a Ga diffusion into the Mo back contact, while no diffusion of In and Cu occurs. Furthermore, we derive a detailed picture of the Na distribution near the back and front side of the Cu(In,Ga)Se, absorber. (C) 2006 Elsevier B.V. All rights reserved.