In the present work, novel gel-based composite polymer electrolytes for lithium batteries were prepared by introducing a hierarchical mesoporous silica network to the poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP)-based gel electrolytes. As compared with the PVDF-HFP-based gel electrolytes with/without conventional nano-sized silica fillers, the novel electrolytes have shown more homogeneous microstructure, higher ionic conductivity and better mechanical stability, which could be caused by the strong silica network and the effective interactions among the polymer, the liquid electrolytes and the silica. Moreover, the cell with this kind of electrolytes could achieve a discharge capacity as much as 150mAhg−1 at room temperature (LiCoO2 as the cathode active material), with high Coulomb efficiency.