We present an investigation of the valence-electron excitation spectra including the collective plasmon modes of SrTiO₃, LaAlO₃ and their heterostructures with non-resonant inelastic x-ray scattering. We analyse the spectra using calculations based on first principles and atomic multiplet models. We demonstrate the feasibility of performing valence IXS experiments in a total reflection geometry. Surprisingly, we find that the plasmon, interband and semicore excitations in multilayers are well described as a superposition of bulk-compound spectra even in a superstructure composing of layers of only one atomic layer thickness.