In this paper we report the structural and optical characterisation of 5 % Pr doped (Bi 0.5 3? Na 0.5 ? ) A Ti B O 3 (BNT) in A and B site of a distorted perovskite structure. The samples of pure and doped BNT were synthesized successfully by conventional solid state sintering method. The samples were sintered at 1100°C for 3 h. The sintered samples are subjected to structural and optical spectroscopy analysis such as Raman, Fourier Transform Infra red (FTIR) and Photoluminescence (PL). The XRD analysis show Pr doping of 5 % causes change in the lattice parameter and a significant change in the structure. In conjunction to XRD, Raman result shows a local structure distortion, in the region of 200-600 cm -1 , which confirms the formation of cluster type phase on Pr doping in both A and B site. Also, the degree of distortion in the structure is significantly high in the case of B site doping. This is confirmed in both XRD and Raman spectra. The UV-Vis spectra shows that Pr doping causes a red shift in the BNT band gap energy due to local distortion in A and B site doping. The PL emission observed at the excitation of 360 nm shows an intense red band on A site Pr doping, were the emission intensity decreases on B site doping. The observed results are discussed and reported.Electronic supplementary material The online version of this article (