In this study, Li2O-HfO2-SiO2-Sm2O3-Au2O3 glasses (doped with fixed concentration of Sm2O3 and varied contents of Au2O3) were synthesized and characterized. The role of Au0 particles on improvisation of red emission of Sm3+ ions was investigated. Optical absorption (OA) spectra of these glasses indicated a number of bands excited from 6H5/2 of Sm3+ ions. A broad band in the greenish-yellow spectral region due to surface plasmon resonance (SPR) of Au0 nanoparticles was also detected in these spectra. Photoluminescence (PL) spectra of (Sm free glasses) embedded with Au0 metallic particles (MPs) showed a wide band in the visible region ascribed to the transition of electrons from sp → d energy bands. Luminescence spectra of Sm3+ doped glasses revealed bright orange and red emission bands with substantial increased intensities with increased concentration of Au2O3. Effect of Au0 MPs on the red emission efficiency of Sm3+ ions was emphasized with kinetic rate equations.