A distinction between amorphous and crystalline silicon by means of the silicon L23-edges acquired by electron energy-loss spectroscopy is presented. Both the fine structures of the L23-edges and their threshold energies have been determined and are compared. Since the zero loss peak and the adjacent core loss edges could not be acquired simultaneously due to their strong difference in intensity, MgO was used as an external reference for the exact and absolute determination of the threshold energies. As a result, the threshold energies of amorphous silicon and crystalline silicon are identical, while the fine structures of the L23 -edges vary significantly. Calculations of the L23 - edges of crystalline silicon are presented in order to provide an explanation for the differences in their fine structures.