Three modifier oxides, MgO, ZnO, and CdO, were mixed with 1.0 mol % of Thulium-doped lead arsenate glasses and were synthesized by the usage of melt-quenching technique. XRD patterns clearly show the evidence that samples are amorphous and had been supported with the aid of using the lack of distinct peaks. Various functional physical parameters such as molar volume, oxygen packing density (OPD), Tm3+ ion concentration, mean Tm3+ ion separation, polaron radius are evaluated by using experimentally measured densities and refractive indices. The optical absorption spectra of PbO–MO (M = Mg, Zn, Cd)–As2O3:Tm2O3 glass system have been studied. Through the application of least square fitting analysis, the J-O phenomenological parameters (Ω2, Ω4, Ω6) for the three glass systems have been calculated.