PbO–Sb 2O 3–B 2O 3 glasses mixed with different content of Pr 2O 3 (ranging from 0 to 0.6 mol%) were crystallized. The samples were characterized by X-ray diffraction, transmission electron microscopy (TEM) and differential scanning calorimetric (DSC) techniques. The TEM studies indicated that the samples contain well defined and randomly distributed nanoclusters possessing the sizes within ∼30–40 nm. The XRD spectra have exhibited diffraction peaks due to presence of Pb 5Sb 2O 8, Pb 3(SbO 4) 2, PbB 4O 7, β-PrSbO 4, Pr 3SbO 7, Pr 3Sb 5O 12 crystalline phases. From these spectra, it was identified that the antimony ions co-exist in Sb 5+ state with Sb 3+ state in the titled glass ceramic samples. The photo-induced birefringence (changes in refractive indices) caused by simultaneous exposure of the sample with the doubled frequency coherent laser beam (1.54 μm and 0.77 μm) was monitored by polarized probing beam of varying wavelength in the range of 750–1250 nm. The induced birefringence exhibited a maximum at about 1000 nm, a wavelength corresponding to 3H 4 → 1G 4 optical excitation transition of Pr 3+ ion. We have established a correlation between the intensity of this transition and the birefringence dispersion. Principal role of the photo-occupation of this transition is identified. The variations of photo-induced birefringence with increase in the content of Pr 2O 3 is explained due to the increasing degree of disorder and increasing concentration of deformed PrO 8 structural units in the glass ceramic. Further analysis of these results coupled with the data on IR and Raman spectral studies, has indicated that PbO–Sb 2O 3–B 2O 3 glasses crystallized with 0.6 mol% of Pr 2O 3 exhibit maximal birefringence effects.