The ongoing scaling-down of semiconductor device structures requires new techniques for cross-sectional thin film characterization. Energy filtering transmission electron microscopy was used for both elemental mapping and electron energy-loss near edge structure (ELNES) mapping of Si compounds. Si, Si3N4 and SiO2 layers could be clearly differentiated by elemental mapping as well as by ELNES mapping. A clear differentiation of the two phases in CoSi/CoSi2 layer stacks was only possible by ELNES mapping. It is shown that specific energy filter settings allows distinction between all the Si compounds using only the Si-L-2,L-3 electron energy-loss edge and the respective electron energy-loss near edge structures.