We present a crack-free optically active SiO2 glass-composite material containing YAG:Ce synthesized by a modified sol-gel technique. A glass-composite material consisting of yttrium aluminum garnet doped with Ce3+ (YAG:Ce) entrapped into a SiO2 xerogel. This composite material has been prepared by sol–gel technique with modified gelation and drying process to obtain crack-free optically active SiO2 glass. The concentration of the YAG:Ce was from 0.5 to 2.0 wt%. All synthesized samples were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques. The luminescence properties of the obtained materials were studied.