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Electrically and thermally induced transitions between ferroelectric and relaxor states are of great importance for Bi1/2Na1/2TiO3 (BNT)-based materials because of their close relevance to electromechanical properties. In this study, the electric field-temperature (E-T) phase diagrams of Fe doped Bi1/2(Na0.8K0.2)1/2TiO3 (BNKT) ceramics are constructed via an experiment and theory combined approach. A novel phenomenological model based on the Landau-Devonshire theory and the Preisach model is proposed to describe the electric field induced phase transitions. Using this model, an approximate free-energy landscape is obtained by fitting the experimental double polarization-electric field loop, and then the electric field representing ferroelectric and relaxor two-phase equilibrium is calculated from the free-energy landscape for the construction of an E-T phase diagram. The constructed E-T phase diagrams meet basic thermodynamics requirements, for example, the Clausius-Clapeyron relation, and, therefore, overcome some of the shortcomings of previously reported E-T phase diagrams for BNT-based ceramics. The relationship between the E-T phase diagram and electromechanical properties is also established. From the E-T phase diagrams, it is predicted that Fe doping could lower the threshold field of triggering giant strains of BNKT ceramics at a high temperature. This prediction is successfully verified by experimental measurement of the electric field induced strain. At the optimized temperature for strain property, the threshold field of triggering giant strain is estimated to be about 2.6 kV/mm for a 3.0% Fe doped sample, significantly lower than 3.5 kV/mm for the undoped sample. This shows that the E-T phase diagram can provide valuable guidance for the improvement of electromechanical properties of BNT-based ceramics.

High‐power piezoelectric ceramics are typically driven to output vibration velocity (v0) under high AC electric fields. Herein, the Fe2O3 doped 0.125 Pb(Zn1/3Nb2/3) O3–0.075 Pb(Mn1/3Nb2/3)O3–0.8 Pb(Zr0.48Ti0.52)O3(PZMNZT–xFe; x = 0.05–0.35) piezoelectric ceramics were prepared to enhance v0, and the favorable comprehensive electrical properties, such as d33 = 315 pC/N, Qm = 1738, kp = 0.58, kt = 0.48, εr = 1156, tan δ = 0.4%, and Tc = 320°C, were achieved in the PZMNZT–0.15Fe ceramic. Most importantly, the PZMNZT–0.15Fe ceramic presented a reliable v0 of 0.90 m/s, which was 2.25 times of the commercial PZT4 ceramic (∼0.40 m/s). The excellent high‐power performance should be attributed to ordering functional elements such as crystal grains and ferroelectric domains. Overall, this work reveals that the PZMNZT–0.15Fe ceramic is competitive for high‐power applications.