Dielectric capacitors play an increasingly important role in modern electronic power systems due to their ultrahigh charging and discharging speeds and power density. Much research has focused on enhancing dielectric breakdown strength to achieve better energy storage performance; however, this increases the potential for heat generation and unexpected insulation failures, thereby affecting the stability and lifespan of devices. This study introduces a small amount of Na+ dopants at the A-site of BaTiO3, inducing lattice distortions and enhancing local polarization to increase energy storage density rather than through enhancing breakdown strength. The introduction of Na+ enhances the ferroelectric properties, with polar nano-regions (PNRs) gradually evolving into long-range ordered large domains. In the Ba0.985Na0.015TiO3 films, the coexistence and coupling of abundant PNRs with a few long-range ordered ferroelectric domains result in high saturation polarization and low residual polarization. At a moderate electric field of 2.3 MV cm−1, an ultrahigh energy density of 44.3 J cm−3 and a high energy storage efficiency of 78.6 % were obtained. Additionally, the film exhibits excellent frequency stability (100 Hz-20 kHz), temperature stability (30–180 °C), fatigue resistance (107 cycles), and high pulsed discharge energy density, along with great thermal stability. This work provides new insights into achieving exceptional energy storage performance in single-phase films.