Polymer–ceramic composite electrolytes are emerging as a promising solution to achieving high ionic conductivity, optimal mechanical properties, and good safety for developing high-performance all-solid-state rechargeable batteries. In this work, we report a garnet (Li7La3Zr2O12)-based hybrid solid electrolyte (HSE) membrane designed for high performance solid-state lithium batteries for the first time. The composite HSE membrane is composed of LLZO particles and PVDF–HFP polymer matrix. The solid-state lithium battery with this HSE membrane, Li metal anode and LiFePO4 cathode exhibits an initial reversible discharge capacity of 120mAhg−1 at a charge/discharge current density of 0.5C at room temperature. This solid-state battery is used to store the energy harvested by a TENG at different rotation rates. The solid state battery can efficiently store the pulsed energy, especially for output at high frequencies.