Piezophotonics is a great interesting field of physics that has led to a number of important technologies, such as light source, smart sensors, and mechatronics. In this work, we reported Pr-doped (Bi0·5Na0.5)TiO3-based lead-free ceramics with strong red photoluminescence emission and large strain response (d33∗ = 460 pm/V, S = 0.32 %). The PL emission can be quenched by decreasing the intensity by 93 % after electrical polarization (E = 50 kV/cm). The local structure and electric field-induced structural changes were systematically investigated to reveal the significant distinction in photoluminescence properties caused by electrical polarization. The results indicated that polarization treatment eliminates the structural inhomogeneities and establishes a long-range ferroelectric tetragonal and rhombohedral distortion. The crystal structure transformed irreversibly from a non-ergodic to a normal ferroelectric state. PL quenching originated from the decreased distortion of octahedral due to the transition from a non-ergodic state to a highly ordered symmetrical structure. Meanwhile, the enlarged domain structure contributed to the photoluminescence quenching effect. Our findings demonstrate that an electric field can be a robust tool for adjusting the photoluminescence property and provide insights into the relationship between the structure and PL properties of BNT-based ceramics under an external stimulus.