In the present investigation, we are reporting the successive ferroelectric relaxor behavior of (Ba,Sr)TiO borosilicate glass ceramics. The ferroelectric relaxor nature of the present glass ceramics is attributed to structural phase transition from the rhombohedral to orthorhombic to tetragonal to cubic. A very high value of dielectric constant was found to be 89,684 at 100 Hz in glass ceramic sample 64[(BaSr)TiO]-30[2SiO-BO]-5[KO]-1[LaO], BST5K1L0.3S831 and such large value may be due to space charge polarization in glassy matrix. The various contribution in polarization processes are confirmed by impedance spectroscopic analysis.