Absorption and electron paramagnetic resonance (EPR) investigations were carried out on barium based alkali borosilicate glasses in order to characterize the oxidation states and coordination behaviour of several transition metal ions in them, namely Cr, Cu, Fe and Mn. The glass composition was similar to that of the Trombay waste base glass used for vitrification of research reactor high level waste (HLW). It xvas observed that Cr is stabilized in the glass matrix in two oxidation states namely 3+ and 5+ hi distorted octahedral geometries. The Racah parameter value was calculated from the absorption studies. Cu ions in the borosilicate glass get stabilized as Cu²⁺ where the lone electron resides in d_x2-y2 orbital. It was found that the Cu ions are interacting via a paramagnetic interaction through the oxygen linkage. From the correlation of the absorption and EPR data, bonding parameters were evaluated for the system. In case of Fe-glass it was found that iron gets stabilized in 3+ oxidation state both in tetrahedral and octahedral geometries. In case ofMn incorporated barium borosilicate glass, it was found out that, apart from the usual 2+ oxidation state, Mn gets stabilized in the matrix in the form MnO₄-  and  MnO₄2-.