A new solid-state ionogel electrolyte was synthesized using a silane coupling agent (SCA) that can spontaneously form a porous network to confine an ionic liquid electrolyte (ILE). We found that epoxy groups grafted on silica can promote the ionic dissociation of a lithium salt and ionic liquid. The ionogel with the optimal molar ratio (ILE/SCA=0.75) exhibited excellent thermal stability, a wide redox stability window, and ionic conductivity of 1.91×10−3 Scm−1 at 30°C, which is higher than that of the pure IL electrolyte. The developed ionogel improved the operating temperature of batteries from room temperature to at least 90°C. Furthermore, the good compatibility of the ionogel with a LiFePO4 cathode and Li4Ti5O12 anode indicates that it can be used as an electrolyte for full battery systems. More importantly, the SCA was employed as an organosilica precursor to synthesize a new solid-state ionogel electrolyte. This new ionogel electrolyte with high stability and capacity represents a considerable advance in solid-state electrolytes for lithium-ion batteries.