Dielectric materials with excellent energy storage performance are urgently needed in advanced electrical power systems. We have reported that Mn2+‐doped SrTiO3 thin films have high energy storage density. However, the thin films exhibit fat polarization‐electric field hysteresis loops with high hysteresis, which is not conducive to greater energy storage performance. In this work, the Ca2+‐doped Sr1‐xCaxTi0.99Mn0.01O3 thin films are fabricated to construct slim polarization‐electric field hysteresis loops with low hysteresis for obtaining excellent energy storage performance. Because Ca2+ can break the long‐range ferroelectric order of SrTi0.99Mn0.01O3, the domain size decreases and the coupling of domains weakens, ultimately leading to low hysteresis. Moreover, doping Ca2+ can induce distortion of the octahedral [TiO6] to form local polarization regions. When doped an appropriate amount of Ca2+, local lattice distortion plays an important role in polarization behavior, which helps to enhance polarization. Meanwhile, the Ca2+‐doped thin films also possess good insulation. Finally, the higher energy storage density of 63.9 J cm‐3 is achieved in the Sr0.9Ca0.1Ti0.99Mn0.01O3 thin film. When the electric field is less than 4000 kV cm‐1, the energy storage efficiency remains above 70%. Simultaneously, a wide working temperature range from ‐100℃ to 100℃ is also obtained.