A family of antimony tellurite glasses of the composition (55‐x)TeO2‐10Sb2O3‐35B2O3 mixed with different concentrations of TiO2 (0 to 2 mol%) were prepared and crystalized. The samples were characterized by XRD and SEM techniques; spectroscopic (optical absorption and Raman) and PIB properties have been investigated. Randomly distributed crystals were identified by SEM. The XRD studies have revealed the presence of Sb2Te2O7, Sb2Te2O9, TiTe3O8,TiBO3 crystalline phases in these samples. The diffraction data also indicated that, the antimony ions coexist in Sb5+ state with Sb3+ state in these samples; however, the concentration of Sb3+ ions seems to be dominant over Sb5+ ions in the samples containing lower concentrations of TiO2. Optical absorption spectral studies have indicated that a considerable proportion of Ti ions do exist in Ti3+ state in addition to Ti4+ state and the redox ratio seems to be increasing with increase in the concentration of TiO2. The Raman spectral studies have revealed the presence of several conventional structural groups viz., TeO4, SbO3, BO3, BO4, TiO4,TiO6 in the glass ceramic network; these studies have also indicated a growing degree of disorder in the glass ceramic with increase in the concentration of TiO2. The experiments on PIB with 7 ns 1064 nm Nd:YAG laser beam indicated the maximum intensity of birefringence for the sample crystallized with 2.0 mol% of TiO2. This result combined with the optical absorption studies allowed us to conclusion that Ti ion surrounding ligands play principal role in the observed PIB effects (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)