With regard to the global energy crisis and environmental pollution, ferroelectric thin films with unique polarization behavior have garnered considerable attention for energy storage and electrocaloric refrigeration. Herein, a series of (1 – x)Bi0.5Na0.5TiO3–xBa(Zr0.2Ti0.8)O3 (x = 0.3–0.9; (1 – x)BNT–xBZT) films were fabricated on Pt(111)/Ti/SiO2/Si substrates. Incorporating BZT can tune the polarization behavior and phase transition temperature of BNT. A high recoverable energy density ≈ 82 J cm–3 and optimized efficiency ≈ 81% were realized for the (1 – x)BNT–xBZT thin film with x = 0.7. The thin film exhibits excellent stability in energy storage performance, a wide working frequency range (0.5–20 kHz), a broad operating temperature window (20–200 °C), and reduplicative switching cycles (107 cycles). In addition, the 0.5BNT–0.5BZT film exhibits a desirable electrocaloric effect with a large adiabatic temperature change (ΔT ≈ −22.9 K) and isothermal entropy change (ΔS ≈ 33.4 J K–1 kg–1) near room temperature under a moderate applied electric field of 2319 kV cm–1. These remarkable performances signify that the (1 – x)BNT–xBZT system is a promising multifunctional electronic material for energy storage and solid-state cooling applications.