The luminescence modulation behavior of lanthanide ion doped materials possesses great potential for applications in sensing, display and anti-counterfeiting devices. Unlike traditional tuning methods for chemical compositions, novel rare-earth doped ferroelectric oxides exhibit attractive luminescence modulation effects via electric polarization engineering, and enrich the development of multifunctional devices. In this work, Sm3+ doped KSr2Nb5O15 ceramics with abundant ferroelectric and luminescent properties were synthesized. The samples show different relaxation behaviors and ferroelectric features upon chemical and structural factors caused by Sm3+ doping, such as average ionic radii, local tolerance factors, and chemical bonds. After polarization at 20 kV/cm for 20 min, a considerable increase (~40%) in the luminescent emission intensity was obtained in 4 mol. % Sm3+ doped KSr2Nb5O15 ceramics. The related luminescence modulation mechanism was attributed to controlling the environmental symmetry around Sm3+ by the electric polarization. © 2021 Elsevier Ltd and Techna Group S.r.l.