Electrostatic energy storage based on dielectrics is fundamental for high-performance electrical systems. However, developing outstanding energy storage capabilities is challenging because the polarization, loss, and breakdown strength are firmly coupled and mutually restrictive. This work proposes a two-pronged strategy to break out the mutual clamp between these performance parameters by modulating the ergodicity and band structures in Aurivillius ferroelectric films. An inserting layer engineering is carried out using Bi4Ti3O12 as matrix and BiAlO3 as inserting layer. The intrinsic ergodic characteristics drive the realization in the arrangements of internal permanent dipoles through a macroscopically reversible interconversion between relaxor and ferroelectric phases, thereby modulating the pinched double hysteresis loops with both large polarization and low hysteresis. Moreover, the band structure associated with the breakdown strength is additionally regulated by orbital hybridization. Thus, ergodic relaxor ferroelectric film Bi5Ti3AlO15, exhibits an excellent energy storage performance with densities reaching as high as ∼131.8 J cm−3 and efficiencies exceeding 73%. This work overcomes the ubiquitous trade-off among polarization, hysteresis, and breakdown strength, offering extra insight into developing dielectric energy storage capacitors.