Lead-free BaTiO3 (BT)-based multilayer ceramic capacitors (MLCCs) with the thickness of dielectric layers ~9 μm were successfully fabricated by tape-casting and screen-printing techniques. A single phase of the pseudo-cubic structure was revealed by X-ray diffraction. Backscattered images and energy-dispersive X-ray elemental mapping indicated the high quality of MLCCs without observation of interaction, wrapping, or delamination. The relaxor state was confirmed by transmission electron microscopy and temperature-dependent permittivity. Impedance spectroscopy at various temperatures revealed the electrical heterogeneous response for MLCCs with high-resistive electrical components. Improved energy storage performance was obtained by multilayering, comparing with the bulk ceramics. Enhanced recoverable energy density ~6.88 J/cm3 with high efficiency ~90% were realized under an electric field of 820 kV/cm, which is mainly attributed to the intrinsic high-resistivity and relaxor behavior. Furthermore, good temperature (20–85 °C) and frequency stabilities (0.5–50 Hz) were observed in the MLCCs, which are attractive for pulsed power applications.