The electrocaloric (EC) effect in ferroelectric materials has been studied extensively to develop materials for solid-state cooling applications. The Na0.5Bi0.5TiO3-based ferroelectric material is selected for this particular application. The Ti4+ of the lead-free Na0.5Bi0.5TiO3 is completely replaced by (Mg1/3Nb2/3)4+ to enhance the dielectric breakdown strength and to observe the EC effect. The lead-free Na0.5Bi0.5(Mg1/3Nb2/3)O3 is synthesized via the columbite route with optimized processing conditions. The material shows a frequency-independent high ferroelectric–paraelectric transition temperature (460 °C) with a slim polarization vs electric field loop. The adiabatic temperature change (ΔT) of the compound is evaluated from the temperature-dependent polarization behavior, and calculated ΔT is ≈ 0.135 K at room temperature. The room-temperature EC strength and leakage current of the material are examined to check its suitability for solid-state refrigeration. © 2022 Elsevier Ltd