Ferroelectric thin film capacitors have large application potential in pulsed-power electronic and electrical systems due to their high-power density and rapid discharge capabilities. Although lead-based dielectrics are promising, the pursuit of eco-friendly, lead-free alternatives is gaining research attention. Here, the Bi and Li co-doped BaTiO3 thin film exhibiting relaxor ferroelectric properties was investigated for its energy storage properties. The fabricated polycrystalline Ba0.85(Bi0.5Li0.5)0.15TiO3 thin film by pulsed laser deposition revealed good breakdown strength (∼4 MV cm−1), a slim ferroelectric loop, and low leakage characteristics suitable for energy storage applications. The film exhibits a significant value of recoverable energy density (∼70 J cm−3) with better frequency and thermal stability. Notably, the better overall performance parameters of the film, including a sizable power density (261 MW cm−3) and a fast discharge rate (150 ns), along with good energy density and breakdown strength, make the material suitable for pulsed-power energy applications.