This work is focused on making a correlation between results obtained by using spectroscopy and microscopy techniques from single and twofold-layer Silicon-Rich Oxide (SRO) films. SRO films single-layer and twofold-layer characterizations were compared considering the conditions as-grown and with thermal treatment at 1100 °C for 60 min in a nitrogen atmosphere. The thickness of the single-layer film is 324.7 nm while for the twofold-layer film it is 613.2 nm; after heat-treated, both thicknesses decreased until 28.8 nm. X-ray Photoelectron Spectroscopy shows changes in the excess-silicon in single-layer SRO films, with 10% in as-grown films and decreases to 5% for the heat-treated films. Fourier Transform Infrared Spectroscopy (FTIR) exhibits three characteristic vibrational modes of SiO2, as well as, the vibrating modes associated with the Si-H bonds, which disappear after the heat treatment. With UV–Vis spectroscopy results we obtained the absorbance and the absorption coefficient for the SRO films in order to calculate the optical bandgap energy (Egopt), which increased with heat-treatment. The energy peaks of the photoluminescence spectra were used to calculate the silicon nanocrystal size, obtaining thus an average size of 1.89 ± 0.32 nm for the as-grown layer, decreasing the size to 1.64 ± 0.01 nm with the thermal treatment. On the other hand, scanning electron microscopy and high-resolution transmission electron microscopy images confirm the thickness of the twofold-layer SRO films as 628 nm for the as-grown layer and 540 nm for the layer with heat-treatment, and the silicon nanocrystal size of 2.3 ± 0.6 nm for the films with thermal treatment.