Silicon nanocrystals synthesized by electron beam (e-beam) evaporation of Si and SiO2 mixture are studied. Rutherford backscattering spectrometry of the as-deposited Si-rich silicon dioxide or oxide (SRO) thin film shows that after evaporation, the Si and SiO2 concentration is well kept, indicating that the e-beam evaporation is suitable for evaporating mixtures of Si and SiO2. The SRO thin films are annealed at different temperatures for two hours to synthesize silicon nanocrystals. For the sample annealed at 1050℃, silicon nanocrystals with different sizes and the mean diameter of 4.5 nm are evidently observed by high resolution transmission electron microscopy (HRTEM). Then the Raman scattering and photoluminescence spectra arising from silicon nanocrystals are further confirmed the above results.