A new type of energy storage devices utilizing multilayer Pb(Zr0.95Ti0.05)0.98Nb0.02O3 films is studied experimentally and numerically. To release the stored energy, the multilayer ferroelectric structures are subjected to adiabatic compression perpendicular to the polarization direction. Obtained results indicate that electrical interference between layers (10–120 layers) during stress wave transit through the structures has an effect on the generated current waveforms, but no impact on the released electric charge. The multilayer films undergo a pressure-induced phase transition to antiferroelectric phase at 1.7 GPa adiabatic compression and become completely depolarized, releasing surface screening charge with density equal to their remnant polarization. An energy density of 3 J cm−3 is successfully achieved with giant power density on the order of 2 MW cm−3, which is four orders of magnitude higher than that of any other type of energy storage device. The outputs of multilayer structures can be precisely controlled by the parameters of the ferroelectric layer and the number of layers. Multilayer film modules with a volume of 0.7 cm3 are capable of producing 2.4 kA current, not achievable in electrochemical capacitors or batteries, which will greatly enhance the miniaturization and integration requirements for emerging high-power applications.