Microstructural properties of the beryllium (Be) and silicon (Si) in periodic multilayer mirrors Be/Si with the variation of film thickness were comprehensively determined by Raman scattering. For the thinner films, the structure of Be evolved in the amorphous phase, and it was transformed into the polycrystalline phase for thicker films. The Si films in the periodic structure were condensed into the amorphous phase. The small fraction of nanocrystalline Si particles was distributed within the amorphous phase. A shake-up satellite peak of Si 2s photoelectrons was observed in X-ray photoelectron spectroscopy which suggested the excitation of a plasmon in Si films embedded within Be/Si periodic multilayers. The energy of plasmons was sensitive to the film thickness of Si in the periods which directly corresponds to the particle size. The binding energy of the satellite peak of Si 2s photoelectrons was blueshifted (higher energy) with a decrease in the particle size. This was explained by size dependent quantum confinement of particles.