Recently, the energy storage density of lead-free ceramics has been improved significantly, however, the single functional material can no longer satisfy the development trend of miniaturization and integration of electronic devices, thus developing multifunctional materials has become an urgent task. In this study, we fabricate a novel multifunctional ceramic with luminescence and energy storage properties, which can be denoted as (1-x)Bi_0.5Na_0.5TiO₃-xSr_0.7Sm_0.2TiO₃ ((1-x)BNT-xSST). The SST is doped into BNT can not only enhances the relaxor ferroelectric (RFE) phase by decreasing tolerance factor (t), but also introduces the luminescent properties due to the exist of Sm³⁺. Encouragingly, all ceramics exhibit strong red photoluminescence and long decay lifetime except BNT. Besides, the ceramic of 0.6BNT-0.4SST exhibits a high recoverable energy storage density (W_rec) of 3.52 J/cm³ and a large power density (P_D) of 220 MW/cm³ simultaneously, implying its large potential in optoelectronic devices application.