AbstractFerroelectric materials under shock compression can generate current and power by a drastic change of the remnant polarizations and surface bound charge. This behavior has been employed in applications involving nuclear fusion trigger, energy storage devices, and high pulse power sources. Despite the large power output in lead‐containing ferroelectrics, lead‐free materials are highly desirable owing to the environmental concerns. Herein, the phase transition behaviors and current outputs of 0.92Bi0.5Na0.5TiO3‐0.08BiAlO3 (BNT‐8BA) materials are studied under high pressure. The BNT‐8BA ferroelectric ceramics can be completely depolarized from polar to the nonpolar state under shock compression, resulting in a current output in the external circuit. The phase‐transition‐induced depolarization pressures of BNT‐8BA are lower than those of the pure Bi0.5Na0.5TiO3 under both dynamic and static high‐pressure loads. These results can allow the understanding of the high‐pressure behavior of BNT‐8BA for application as ferroelectric pulsed power supply.