Pr3+-doped SrBi2Nb2O9 (SBN) multifunctional ceramics were synthesized by the conventional solid state method. The photoluminescence (PL) excitation and emission spectra, enhanced ferroelectric and dielectric properties were investigated. The X-ray diffraction (XRD) and FESEM analyses indicated that the samples were simple phase and uniform flake-structure. Under the 250–350 nm ultraviolet (UV) excitations, the red emission was obtained and the optimal emission intensity was investigated when Pr doping level was 0.005 mol. With the increasing of the Pr3+ ion contents, the ferroelectric properties were enhanced obviously. As a new multifunctional material, the Pr3+-doped SBN ceramics could be used for a wide range of application, such as integrated electro-optical devices.