An amorphous Si (a-Si) film, 60 nm thick, embedded between SiO2 layers and deposited on quartz substrate was crystallized in the regime of light-induced solid-phase crystallization (LISPC). The high quality of the film after LISPC was proved by high-resolution transmission electron microscopy (HRTEM), by Raman spectroscopy (RS) measurements, and by electron energy loss spectroscopy (EELS). The crystallized film consisted of fully crystalline grains with lateral sizes of 200–600 nm. Only a few stacking faults and/or dislocations were detected inside these grains. Besides the large grains, regions with fully crystalline material containing a higher density of lattice defects were also observed. An intermixing of phases, i.e., SiO2 or a-Si clusters inside the crystallized Si film and/or Si-clysters inside the SiO2 layers, was not detected.