Multi-component CaF2–Bi2O3–P2O5–B2O3 glasses doped with different concentrations of Cr2O3 were crystallized through heat treatment. The prepared glass ceramic samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and differential thermal analysis (DTA). Spectroscopic studies viz., optical absorption, Fourier transform infrared (FTIR), Raman and electron paramagnetic resonance (EPR) were carried out. The XRD, SEM and DTA studies indicated that the samples contain different crystalline phases. Results of optical absorption and EPR studies pointed out the gradual conversion of chromium ions from Cr3+ state to Cr6+ state with an increase of Cr2O3 content from 0.1 to 0.5mol%. The results of FTIR, Raman and EPR studies revealed that Cr6+ ions participate in the glass network in tetrahedral positions and seemed to increase the polymerization of the glass ceramics. The quantitative analysis of results of the spectroscopic studies further indicated that the glasses crystallized with low concentration of Cr2O3 are favourable for solid state laser devices.