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Sm3+ doped Sr1.90Ca0.15Na0.9Nb5O15 (SCNN: xSm3+) multifunctional ferroelectric ceramics with pure tetragonal tungsten bronze phase were synthesized via the conventional solid-state reaction method. The dielectric, ferroelectric characteristics and luminescent behaviors were systematically studied. The electrical properties suggested that a moderate Sm3+ doping could enhance the electrical performances. The orange-reddish emission originated from the transition of 4G5/2 → 6H7/2, 4G5/2 → 6H5/2 and 4G5/2 → 6H9/2 was observed under excitation wave of 406 nm. The strongest emission intensities were obtained at the Sm3+ doping content of 0.010. The degree of thermal quenching for the composition with x = 0.010 was relatively lower and the normalized emission intensity continued still 80% from room temperature to 150 °C. Besides, the transmittance in visible spectra of the SCNN: xSm3+ ceramics could be improved obviously, which was up to 50% at the doping amount of 0.010. These results show that the SCNN: xSm3+ multifunctional ferroelectric niobates have promising potential in electric-optical devices. [ABSTRACT FROM AUTHOR]