0.94(Na_0.5Bi_0.5TiO₃)-0.06BaTiO₃ ferroelectric thin films with and without the Pb_0.8La_0.1Ca_0.1Ti_0.975O₃ seed layer were deposited on platinum-buffered silicon substrates by using Sol–Gel process. The influence of Pb_0.8La_0.1Ca_0.1Ti_0.975O₃ seed layer and annealing temperatures on the microstructures, ferroelectric properties and energy-storage performances of the as-prepared films were investigated in details. The low annealing temperature and Pb_0.8La_0.1Ca_0.1Ti_0.975O₃ seed layer could improve the values of electric break-down field strength and P_max-P_r, which play a vital role for high recoverable energy-storage density. Owing to the high electric break-down field strength value of 3310 kV/cm, a large recoverable energy density of W=17.2 J/cm³ and a high energy efficiency of η=74.3% were obtained for the 0.94(Na_0.5Bi_0.5TiO₃)-0.06BaTiO₃ thin film with the Pb_0.8La_0.1Ca_0.1Ti_0.975O₃ seed layer, which was annealed at 450 °C.