Recent progress in “water-in-salt” electrolytes (WiSE) and “hybrid aqueous/non-aqueous electrolytes” made supporting more choices about active materials is possible, because of which expanded Electrochemical stability window (ESW). As a result of, exploring high energy density aqueous Li-ion batteries (ALBs) is a meaningful research point. However, forming unstable passivation layer on cathode side obstructs high energy cathode materials (e.g. layered structure cathode) were utilized in those electrolytes, since their intrinsic instability in aqueous environment. Herein, a new organic specie was introduced into hybrid electrolyte to form stable and uniform CEI on cathode surface. Ethoxy-(pentafluoro)-cyclotriphosphazene (PFN), the contribution of the PFN component on the electrochemical performance and CEI film formation composition was systemically investigated in NCM622 || TiO2@LiTi2(PO4)3 full-cells. Adding of this component can decrease viscosity of highly concentrated electrolyte and form novel solvation structure, which take part into CEI formation and consolidate it. This stabilization approach enables the utilization of layered structured cathode materials in hybrid electrolytes for ALIBs.