Na 2 O–PbO–Al 2 O 3 –B 2 O 3 (NPAB) glasses mixed with different concentrations of WO 3 (ranging from 0 to 2.5mol%) are synthesized by conventional melt quenching method. The samples are characterized by X-ray diffraction (XRD), optical absorption, Electron paramagnetic resonance (EPR) and Fourier transform infrared (FT-IR) spectroscopic techniques. Glass formation is confirmed by X-ray diffraction spectra. The optical absorption spectra of these glasses exhibited a predominant broad band peak at about 850–870nm is identified due to d xy –d x 2 −y 2 transition of W 5+ ions. From the optical absorption spectral data, optical band gap (E opt ) and Urbach energy (ΔE) are evaluated. From EPR spectra the strength of the signal is increased and hyperfine splitting is resolved with increasing concentration of WO 3 in the glass matrix. The FT-IR spectral studies have pointed out the existence of conventional BO 3 , BO 4 , B–O–B, PbO 4 , WO 4 and WO 6 structural units of these glasses. Various physical properties and optical basicity are also evaluated with respect to the concentration of WO 3 ions.