Substituting conventional electrolyte for redox electrolyte has provided a new intriguing method for extending battery life. The efficiency of utilizing the contained redox species (RS) in the redox electrolyte can benefit from increasing the specific surface area of battery electrodes from the electrode side of the electrode-electrolyte interface, but is not limited to that. Herein, a new strategy using nanocomposite electrolyte is proposed to enlarge the interface with the aid of nanoinclusions from the electrolyte side. To do this, graphene oxide (GO) sheets are first dispersed in the electrolyte solution of tungstosilicic salt/lithium sulfate/poly(vinyl alcohol) (SiWLi/Li2SO4/PVA), and then the sheets are bridged to electrode, after casting and evaporating the solution on the electrode surface. By applying in situ conductive atomic force microscopy and Raman spectra, it is confirmed that the GO sheets doped with RS of SiWLi/Li2SO4 can be bridged and electrically reduced as an extended electrode-electrolyte interface. As a result, the RS-coated GO sheets bridged to LiTi2(PO4)3//LiMn2O4 battery electrodes are found to deliver extra energy capacity (∼30 mAh/g) with excellent electrochemical cycling stability, which successfully extends the battery life by over 50%.