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We investigate the growth performance of tin oxide on the Si substrate, achieved by spray pyrolysis using the sensitive analysis techniques X-Ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES). These complementary techniques confirm the growth of homogeneous SnO2 thin films. We also study the electronic distribution of the valence band of SnO2 theoretically using density functional theory (DFT). The chemical and physical properties of the material depend on the electron structure varying as a function of energy. The density of states (DOS) is calculated using the modified Becke–Johnson-Generalized Gradient Approximation (mBJ-GGA) in order to identify the electronic orbitals and the importance of their contribution to the electronic structure of the valence band. Furthermore, we use the experimental technique UV Photoelectron Spectroscopy (UPS) for studying the electronic distribution within the valence band and for validating the theoretical results of the density of states of SnO2/Si.