Pr-doped BiFeO3 ceramics with x ≤ 0.20 were synthesized by a solid-state reaction method. X-ray diffraction patterns of these samples have shown single-phase rhombohedral structure with R3c space group symmetry. Remanent magnetization has been found to increase with Pr concentration. Magnetization versus temperature plots for x = 0.0 and 0.20 exhibit a broad magnetic anomaly at around 375 and 393 °C, respectively, indicating the Neel temperature “TN”. Dielectric constant (ϵr) versus T plots exhibit dielectric anomalies at around 375 °C in these materials, which may correspond to the transition temperature TN. The photoluminescence spectra of these ceramics exhibit band-edge emission in the blue region and defect-related emission in the green region. The FTIR spectra show two broad vibrational modes at 430 and 560 cm−1.