Zinc tin oxide (Zn1−xSnxOy) has been proposed as an alternative buffer layer material to the toxic, and light narrow-bandgap CdS layer in CuIn1−x,GaxSe2 thin film solar cell modules. In this present study, synchrotron-based soft X-ray absorption and emission spectroscopies have been employed to probe the densities of states of intrinsic ZnO, Zn1−xSnxOy and SnOx thin films grown by atomic layer deposition. A distinct variation in the bandgap is observed with increasing Sn concentration, which has been confirmed independently by combined ellipsometry-reflectometry measurements. These data correlate directly to the open circuit potentials of corresponding solar cells, indicating that the buffer layer composition is associated with a modification of the band discontinuity at the CIGS interface. Resonantly excited emission spectra, which express the admixture of unoccupied O 2p with Zn 3d, 4s, and 4p states, reveal a strong suppression in the hybridization between the O 2p conduction band and the Zn 3d valence band with increasing Sn concentration.