The trivalent gadolinium, doped lead-lead dioxide glass, with the chemical composition xGd2O3•(100 − x) [4PbO2•Pb], where x= 10–50 mol% Gd2O3 have been successfully fabricated by conventional melt quenching technique, and investigated by X-ray diffraction, Fourier Transform Infrared, Electron paramagnetic resonance, Ultraviolet-Visible, and Photoluminescence spectroscopy for their structural, optical, and luminescence properties. The X-ray diffraction indicated high solubility of rare-earth. The high addition of Gd2O3 content generates changes of basic [PbOn] structural units. Electron paramagnetic resonance spectrum confirms the presences of the gadolinium as a Gd3+ in the lead host matrix. The formation of the non-bridging oxygens and chemical bonds is dependent upon the Gd2O3 content, Gd3+ ions environment, and its distribution in the glass. Under the 395 nm excitation, emissions corresponding to 6GJ → PJ and 6GJ → IJ transition of Gd3+ ions, were observed. The CIE color coordinates, suggested that Gd3+ activated lead-lead dioxide glasses is suitable for warm orange luminescence applications.