Poly (ethylene oxide) (PEO)-based solid-state polymer electrolytes (SPEs) show prospects in all-solid-state lithium metal batteries. However, they suffer from low ionic conductivity at room temperature and interfacial instability with high voltage cathodes for long-term cycling. In this work, top-down fluorinated PEOs (F-PEOs) for the all-solid-state electrolytes, which are scalable and cost-effective, are developed to improve the battery performance. We demonstrate, that by enhancing the disordering of the F-PEO matrix, the SPE achieves a maximum Li+ conductivity of 1.1 × 10−4 S cm−1 at 40 °C, which is 20 times higher than the baseline. By forming robust cathode/SPE and Li/SPE interfaces, the F-PEO-based SPEs demonstrate stable cycling in the LiFePO 4 /Li and LiNi 0 · 8 Mn 0 · 1 Co 0 · 1 O 2 /Li (3–4.4 V, 500 cycles, capacity retention of 91.6%) based all-solid-state batteries at 40 °C. Furthermore, our work highlights the significance of "disordering engineering" for energy storage materials. • Top-down direct fluorinated PEOs(F-PEOs)are developed as the matrix for SPEs. • The regularity of the polymer and the degree of crystallinity are reduced. • Enhancement of ionic conductivity (∼20 times higher than the baseline). • Robust cathode/SPE and Li/SPE interfaces are formed. • The NMC811/Li all-solid-state cells can cycle stably at 40 °C for 500 cycles. [ABSTRACT FROM AUTHOR]