Here we demonstrate an oxidative process to control metallic bismuth (Bi 0) nanoparticles (NPs) creation in bismuth glass nanocomposites by using K 2S 2O 8 as oxidant and enhanced transparency of bismuth glasses. Formation of Bi 0 NPs has been monitored by their distinct surface plasmon resonance (SPR) band at 460 nm in the UV–visible absorption spectra. It is further confirmed by the transmission electron microscopy (TEM) images which disclose the formation of spherical Bi 0 NPs whereas the selected area electron diffraction (SAED) pattern reveals their crystalline rhombohedral phase. These glasses are found to exhibit visible and near infrared (NIR) luminescence bands at 630 and 843 nm respectively on excitation at 460 nm of the SPR band. It is realized that the luminescence center of bismuth species is an uncertain issue, however, it is reasonable to consider that the emission band at 630 nm is due to the combination of 2D 5/2 → 4S 3/2 of Bi 0 and 2P 3/2 (1) → 2P 1/2 of Bi 2+ transitions, and that of NIR emission band at 843 nm is attributed to the 2D 3/2 → 4S 3/2 of Bi 0 transition.