Surface-modified BaTiO3 of 230[Formula: see text]nm average grain size were synthesized by coating BaTiO3 particles with 3[Formula: see text]wt.% Al2O3 and 1[Formula: see text]wt.% SiO2. Ceramic films of different thicknesses were prepared via tape casting and laminating processes followed by two-steps sintering method. After sintering, the average grain size of Surface-modified BaTiO3 ceramic slightly increased to 275[Formula: see text]nm, and great enhancement of AC breakdown strength (BDS) from 184[Formula: see text]kV/cm to 665[Formula: see text]kV/cm was obtained as the thickness of ceramic films decreased from 63[Formula: see text][Formula: see text]m to 12[Formula: see text][Formula: see text]m, resulting in improvement of discharge energy density from 1.14[Formula: see text]J/cm3to 4.06[Formula: see text]J/cm3. Because of their low-cost, easily fabrication, lead-free, improved AC BDS and discharge energy density, surface-modified BaTiO3 ceramic films appeared promising for applications in multilayer energy storage capacitors.