Na2O-Sb2O3 glasses doped with different concentrations of Au2O3 were prepared by melt quenching technique and later were heat treated at 800 degrees C for 6hours. Structural analysis by XRD, XPS, SEM, EDS, and DSC techniques indicated that the samples are embedded with multiple crystallites composed of Sb3+, Sb5+, Au3+ ions, and Au-0 metallic particles. These studies have further demonstrated a gradual increasing fraction of Au-0 metallic particles with increasing Au2O3 concentration. IR spectral studies suggested increasing the degree of polymerization of the glass network (due to increasing concentration of Sb5+ ions that participate in the glass network with (SbO4)-O-V structural units) with rise in the concentration of Au2O3. Optical absorption spectra of the titled samples have exhibited a broad absorption band at about 530nm predicted due to the surface plasmon resonance (SPR) and exhibited a spectral red shift with increasing intensity with increase in Au2O3 content. Photoluminescence (PL) spectra of the samples recorded (at (exc)=corresponding SPR band position) exhibited an emission peak at about 580nm (identified as being due to interband transition between sp and d bands of gold particles). Overall, the analysis of these results has confirmed increasing concentration of Au metallic particles with increase in Au2O3 content in the titled material. Finally, it is predicted that the presence of higher concentration of gold particles in the polymerized antimonate glass network makes the materials useful for designing different nano dimensional optoelectronic devices.