AbstractAchieving substantial electrostrain alongside a large effective piezoelectric strain coefficient (d33*) in piezoelectric materials remains a formidable challenge for advanced actuator applications. Here, a straightforward approach to enhance these properties by strategically designing the domain structure and controlling the domain switching through the introduction of arrays of ordered {100}<100> dislocations is proposed. This dislocation engineering yields an intrinsic lock‐in steady–state electrostrain of 0.69% at a low field of 10 kV cm−1 without external stress and an output strain energy density of 5.24 J cm−3 in single‐crystal BaTiO3, outperforming the benchmark piezoceramics and relaxor ferroelectric single‐crystals. Additionally, applying a compression stress of 6 MPa fully unlocks electrostrains exceeding 1%, yielding a remarkable d33* value over 10 000 pm V−1 and achieving a record‐high strain energy density of 11.67 J cm−3. Optical and transmission electron microscopy, paired with laboratory and synchrotron X‐ray diffraction, is employed to rationalize the observed electrostrain. Phase‐field simulations further elucidate the impact of charged dislocations on domain nucleation and domain switching. These findings present an effective and sustainable strategy for developing high‐performance, lead‐free piezoelectric materials without the need for additional chemical elements, offering immense potential for actuator technologies.