This article analyzes electron energy-loss near-edge fine structures of the SrO(SrTiO(3))(n=1) Ruddlesden-Popper system and of the parent compounds SrTiO(3) and SrO by comparison with first principles calculations. For that, the fine structures of chemical solution deposited Ruddlesden-Popper films have been experimentally recorded by means of transmission electron microscopy. Moreover, density of states computations using an all-electron density-functional code have been performed. It is shown that the appearance and shape of the experimental O-K and Ti-L(2,3) fine structure features result from the crystallography-dependent electronic structure of the investigated oxides, which display technologically interesting dielectric as well as lattice-structural properties.