Glass system of composition (50−x)TeO 2 –5Sb 2 O 3 –45B 2 O 3 : xMnO with ‘x’ ranging from 0.3 to 1.5mol% has been prepared via melt quenching followed by controlled crystallization. Further, the samples were characterized by X-ray diffraction, scanning electron microscopy and DSC techniques. A number of studies viz., optical absorption, EPR, and luminescence of these glass ceramics have been carried out. The spectroscopic studies have confirmed the existence of manganese ions in trivalent state in addition to divalent. EPR spectra of all investigated glass ceramics exhibit resonance signals that are characteristic for Mn 2+ ions. The changes found in all the properties as function of the crystallizing agent (MnO) have been discussed in detail.