NaNbO 3 -based lead-free ceramics are gaining widespread interest in recent years due to their environmental friendliness and low density, which can meet the needs of future advanced pulse power electronics for low cost, miniaturization and integration. However, a reversible phase transition of FE-AFE at room temperature for pure NaNbO 3 ceramic will produce a large residual polarization, resulting in a low energy storage capacity. In this work, the ternary system (1- x )(0.92NaNbO 3 -0.08Bi(M g0.5 Ti 0.5 )O 3 )- x CaTiO 3 was designed by introducing the linear material CaTiO 3 doped into (0.92NaNbO 3 -0.08Bi(Mg 0.5 Ti 0.5 )O 3 ) ceramics to enhance the disorder of A/B sites in the system. The introduce of CaTiO 3 could optimize the relaxation characteristics of the ceramics, refine the grain size to improve the breakdown field strength( E b ), which enhance the energy storage properties to W rec  = 5.71 J/cm 3 and η  = 85.7% at 475 kV/cm. Additionally, the 0.8(0.92NN-0.08BMT)-0.2CT ceramic achieves both temperature (20–160 °C) and frequency (5 Hz -120 Hz) stability, while also obtains excellent charge/discharge performance( C D  = 607.22 A/cm 2 , P D  = 48.58 MW/cm 3 , t 0.9  = 28 ns), which indicates the great potential application in pulsed power capacities. Graphical Abstract