Glass samples of undoped and CuO-doped barium borate host glasses were prepared. Combined optical properties together with structural FTIR spectral analysis were measured before and after gamma irradiation with a dose of 6 M rad. The optical spectral absorption of the base is characterized by prominent ultraviolet band which is correlated with trace ferric ions present as impurities. The CuO-doped glasses exhibit an extended broad visible –near IR band which is assumed to originate from octahedrally coordinated Cu2+ ions revealing obvious separation to two component peaks. The irradiation process is accompanied by an increase of the intensities of the absorption bands and can be attributed to proposed photochemical reactions between liberated electrons and formed positive holes with trace iron impurities. FTIR spectra reveal distinct two characteristic broad bands within the mid region 800-1200 cm-1 and 1200-1600 cm-1 indicating the presence of both tetrahedral borate groups and co-presence of triangular borate groups and the intensities of these two IR broad bands increase with the CuO content due to suggested polymerization of the borate network or changes in the ratio of BO4 and BO3 groups.