Li₇La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) and polyvinylidene fluoride (PVDF) composite electrolytes (LPCEs) with a high ceramic content up to 80 wt% have been developed. Hot pressing can significantly reduce the porosity of LPCEs and increase the conductivity to 1.08 × 10⁻⁴ S cm⁻¹ at 60 °C, then the LPCEs can sustain Li plating/stripping cycling for over 1500 h, and make LiFePO₄/LPCE/Li cell display a capacity retention of 86% in 200 cycles.