Pr-substituted BiFe0.8Ti0.2O3 ceramics having compositions Bi1−xPrxFe0.8Ti0.2O3 (x = 0.05, 0.10, 0.15) were synthesized by the conventional solid-state reaction method. XRD pattern indicated that the morphotropic phase boundary was observed for x = 0.05–0.15 samples along with a combination of rhombohedral and orthorhombic phase. Raman spectra confirmed phase transition from rhombohedral to orthorhombic structure for x = 0.05–0.15 samples. All samples showed weak ferromagnetic behaviour attributing that codoping successfully suppressed spiral spin structure by changing the canting angle of BFO. All samples showed tunable optical properties with a variation of optical band gap from 2.13 to 2.2 eV attributing their utilization in photocatalytic activity in visible range.