PbO-As2O3 glasses containing different concentrations of Cr2O3 (ranging from 0 to 0.4 mol% ) were prepared. The differential thermal analysis, IR and optical absorption spectral studies of these glasses were carried out; from these studies, the variations in the values of glass transition and crystallization temperatures, optical band gap and the shifting of symmetrical bending vibrational frequency band were observed with increase in concentration of Cr2O3. Magnetic susceptibilities for these glasses were also determined and Cr3+ ion concentration was estimated. In addition, detailed studies on dielectric properties viz., dielectric constant ε, loss tan δ, ac conductivity $\sigma_{\rm ac}$ and dielectric breakdown strength were investigated. Using the results of these studies, the structural modifications taking place in the glass network were discussed in the light of Cr3+ ion concentration.