One of the most recent developments in the area of modern optics arises due to perovskite materials. The ABO3 perovskite materials like bismuth ferrite is an appealing alternative for various optical devices. Hence, in the present study, Praseodymium (Pr) and Manganese (Mn) co-substituted bismuth ferrite ceramics are prepared by the modified sol-gel method and the correlation between structural and optical properties with the variation in co-substitution concentration has been investigated. Rietveld refinement of X-ray diffraction patterns demonstrates a structural phase change in crystal symmetry from rhombohedral to orthorhombic phase with the increase in concentration for x ≥ 0.025. Lattice deformation in the co-substituted samples is confirmed by Fourier Transform Infrared (FTIR) and Raman spectra. UV–vis diffuse reflectance spectra confirm the strong absorption of light in the visible region. Furthermore, optical energy band gap decreases from 1.95 eV to 1.50 eV with increase in concentration from x = 0.000 to x = 0.100. The refractive index attains the maximum value i.e. 6.16 for x = 0.025 whereas it drops to minimum value of 4.06 for x = 0.100. This demonstrates that the structural modification in bismuth ferrite can be used to tune its optical parameters for the device applications.