This research delves into the influence of red lead content on the red and NIR emission characteristics of Pr3+ ions within a nonconventional antimony silicate glass system. The glasses were synthesized across a composition spectrum of (40 − x) Pb3O4‒49Sb2O3‒(10 + x)SiO2:1Pr2O3, where x ranged from 0 to 35 mol%. Characterization was carried out using XRD, DSC, XPS, and IR spectroscopy. These analyses unveiled the presence of antimony ions in both Sb3+ and Sb5+ states and lead ions in Pb4+ and Pb2+ states within these glass compositions. Optical absorption and emission spectra (at λexc = 445 nm) were recorded within the wavelength range of 400‒1800 nm. Luminescence decay profiles of two pivotal transitions, namely, 3P0 → 3F2 (red emission) and 1G4 → 3H5 (1.3 µm NIR emission), were also recorded. Various radiative parameters from these spectra were extracted using the J–O theory. The findings indicated that, as the Pb3O4 content declined from 40 to 10 mol%, the covalent nature of the samples diminished, resulting in a remarkable amplification in the intensity of both the red and NIR emission bands of Pr3+ ions. The glass containing 10 mol% of Pb3O4 exhibited the most elevated radiative parameters and quantum efficiency. This augmentation was attributed to the reduction of Pb4+ and Sb5+ ions within the glass network or the augmentation of Pb2+ ions, serving as modifiers that mitigated phonon losses. Consequently, glasses with 10 mol% Pb3O4 demonstrate great potential for telecommunications applications, owing to their significant enhancement in PL emission for the 3P0 → 3F2 and 1G4 → 3H5 transitions.