Bi0.5Na0.5TiO3-0.06BaTiO3 (BNT-BT) thin films were prepared by both chemical solution (CSD) and pulsed laser deposition (PLD). The microstructure, dielectric, and ferroelectric properties were investigated. High stability of the dielectric permittivity (∆ɛ/ɛ(150 °C) ≤ ± 15%) over a wide temperature range from room temperature to 300 °C was obtained. Distinctly, the CSD film showed high TCC stability with variation of ± 5% up to 250°C. Furthermore, the CSD film showed an unsaturated ferroelectric hysteresis loop characteristic of the ergodic relaxor phase, however the PLD one exhibited almost saturated loop signature of the coexistence of both ergodic and non-ergodic states. The energy storage properties of the prepared films were determined using the P–E loops obtained at different temperatures. The results showed that these films exhibit stable and improved energy storage density comparable to the ceramic capacitors. Moreover, the CSD film exhibited more rigidity and better energy storage density that exceeds 1.3 J/cm3 under low applied field of 317 KV/cm as well as interesting efficiency in a large temperature range. The obtained results are very promising for energy storage capacitors operating at high temperatures.