(1‐x)Na0.5Bi0.5TiO3‐xNaNbO3 (x = 0.02, 0.04, 0.06, and 0.08) ceramics were fabricated by solid‐state reaction. High‐resolution synchrotron x‐ray powder diffraction (SXPD) data, coupled with macroscopic electromechanical measurements, reveal the occurrence of an electric field‐induced irreversible crystallographic transformation for x = 0.02 and 0.04, from a pseudo‐cubic non‐ergodic relaxor to a rhombohedral or coexisting rhombohedral‐tetragonal long range‐ordered ferroelectric phase, respectively. The highest unipolar electrostrain, corresponding to an effective longitudinal piezoelectric strain coefficient of approximately 340 pm V−1, was obtained for x = 0.04; this effect is attributed to enhanced domain switching as a result of the co‐existing rhombohedral and tetragonal phases for this composition, which is critical for piezoelectric actuator applications.