The Eu3+-modified Bi0.5Na0.5TiO3 (BNT) ceramics have been fabricated by the solid-state reaction method. The impact of Eu3+ doping on the structure, photoluminescence, and electrical properties has been studied by XRD, SEM, PL spectra, and LCR meter. X-ray diffraction analysis reveals that the crystal structure of the samples is well matched with the trigonal perovskite, and the optimal temperature of presintering is 880 degrees C. The Eu3+-doped BNT ceramics show excellent red fluorescence at 614nm corresponding to the D-5(0)-> F-7(2) transition of Eu3+ under 466nm excitation and relatively long fluorescence lifetime. The BNT-0.02Eu ceramic density is up to 5.68g/cm(3) and the relative density is up to 94.6% with sintering temperature 1075 degrees C. The piezoelectric constant (d(33)) of samples has been significantly improved up to 110pC/N by Eu3+ doping. The BNT-0.03Eu ceramic presintered at 880 degrees C and sintered at 1050 degrees C has good dielectric properties and excellent luminescence properties. Eu3+-doped BNT ceramics make it potential applications for novel integrated electro-optical and multifunctional devices.