The poly (vinylidene fluoride) (PVDF)-based composite solid-state electrolyte (CSE) has garnered attention due to its excellent comprehensive performance. However, challenges persist in the structural design and preparation process of the ceramic-filled CSE, as the PVDF-based matrix is susceptible to alkaline conditions and dehydrofluorination, leading to its incompatibility with ceramic fillers and hindering the preparation of solid-state electrolytes. In this study, the mechanism of dehydrofluorination failure of a PVDF-based polymer in the presence of Li₂CO₃ on the surface of Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) is analyzed, and an effective strategy is proposed to inhibit the dehydrofluorination failure on the basis of density functional theory (DFT). We introduce a molecule with a small LUMO–HOMO gap as a sacrificial agent, which is able to remove the Li₂CO₃ impurities. Therefore, the approach of polyacrylic acid (PAA) as a sacrificial agent reduces the degree of dehydrofluorination in the PVDF-based polymer and ensures slurry fluidity, promoting the homogeneous distribution of ceramic fillers in the electrolyte membrane and enhancing compatibility with the polymer. Consequently, the prepared electrolyte membranes exhibit good electrochemical and mechanical properties. The assembled Li-symmetric cell can cycle at 0.1 mA cm⁻² for 3500 h. The LiFePO₄‖Li cell maintains 91.45% of its initial capacity after 650 cycles at 1C, and the LiCoO₂‖Li cell maintains 84.9% of its initial capacity after 160 cycles, demonstrating promising high-voltage performance. This facile modification strategy can effectively improve compatibility issues between the polymer and fillers, which paves the way for the mass production of solid-state electrolytes.