We fabricated GaAs/SiO2 nanocomposite films at room temperature via the sequential sputtering of very thin layers of GaAs and SiO2, which resulted in GaAs nanoparticles uniformly dispersed in a SiO2 glass matrix. The high-resolution transmission electron microscopy (HRTEM) examination showed that the diameter of GaAs nanoparticles embedded in SiO2 matrix depended on the nominal thickness of the GaAs layers. The blue-shift of the absorption edges gave not only the corroborating evidence for the systematic variation of the GaAs-nanoparticle size but also enabled us to estimate the diameter of GaAs nanoparticles quantitatively, which turned out to be consistent with the HRTEM observation. In addition to confirming the results of stylus, HRTEM, and Rutherford backscattering spectrometry (RBS) measurements, the analysis of variable-angle spectroscopic ellipsometry (VASE) spectra based on the effective medium theory revealed an interesting size-dependence of the complex refractive index of the GaAs nanoparticles.