AbstractComposite polymer electrolytes are systems of choice for future solid‐state lithium metal batteries (LMBs). Poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) is among the most interesting matrices to develop new generation quasi‐solid electrolytes (QSEs). Here it is reported on nanocomposites made of PVDF‐HFP and pegylated SiO₂ nanoparticles. Silica‐based hybrid nanofillers are obtained by grafting chains of poly(ethylene glycol) methyl ether (PEG) with different molecular weight on the surface of silica nanoparticles. The functionalized nanofiller improves the mechanical, transport and electrochemical properties of the QSEs, which show good ionic conductivity values and high resistance against dendrite penetration, ensuring boosted long and safe device operation. The most promising result is obtained by dispersing 5 wt% of SiO₂ functionalized with short PEG chains (PEG₇₅₀, Mw = 750 g mol⁻¹) in the PVDF‐HFP matrix with an ease solvent‐casting procedure. It shows ionic conductivity of 0.1 mS cm⁻¹ at 25 °C, more than 250 h resistance to stripping/plating, and impressive results during cycling tests in LMB with LiFePO₄ cathode.