<p>Flexible materials capable of transducing mechanical signals into electrical responses underpin advances in wearable systems, soft robotics, and underwater sensing technologies. Ceramic–polymer piezoelectric composites can combine high electromechanical activity with mechanical compliance, but controlling phase distribution and architecture remains challenging. Here, we report an ethanol-assisted freeze-casting strategy that endows soft lead zirconate titanate/polydimethylsiloxane composites with an anisotropic architecture, enabling both high piezoelectric performance and excellent mechanical deformability. The composites achieve a high piezoelectric charge coefficient of 275 pC·N⁻¹, a piezoelectric voltage coefficient of 233 mV·m·N⁻¹, and an energy-harvesting figure of merit of 64.1 pm²·N⁻¹. The composites also exhibit robust mechanical flexibility, sustaining bending with radii below 5 mm, twisting, compressive deformation, and tensile strains up to 60%. The ethanol-assisted route suppresses freeze-induced cracking and improves three-dimensional compositional uniformity. This method offers a scalable and practical route for fabricating high-performance flexible piezoelectric composites for next-generation sensing technologies.</p>