Various glass compositions were prepared in a glassy system [25BaCO 3-(10-x) ZrO 2-20TiO 2-45SiO 2-xCrO 3 ] (x = 0, 2, 4, and 6) using melt-quenching technique. XRD patterns of glass and glass ceramics showed amorphous and crystalline nature. Density of glass and glass ceramics decreased from 3.4553 to 3.4381 g/cm 3 and 3.7485 to 3.1977 g/cm 3 with increasing concentration of CrO 3. DTA of the glasses revealed a shift in base line which suggests a change in specific heat and attributed to the glass transition temperature, T g. FTIR and Raman spectroscopic analysis indicated that an increasing doping of CrO 3 changes structural network by increasing number of nonbridging oxygens (NBO) within glassy matrix. These results revealed that bands toward low frequency side endorsed to the vibration of Ba 2+ metal cation, bending vibration of Si-O-Si and bonding formation of ZrO 2. Concentration of CrO 3, changed the microsture significantly and hence, a denser, fully developed mixed morphology was noticed with spherical grains of ZrO 2 , irregular shape of bazirite (BaZr 0.97 Ti 0.03 Si 3 O 9) phase and TiO 2 grains. Glass ceramic sample BZTS6C971 CrO 3 (x = 6) retains high value of dielectric constant, ~4555 due to space charge polarization. Hence, these glass ceramics might be useful for diverse applications such as in optical devices, electronic circuits, and multilayer ceramic capacitors.