The poly(vinylidene co-hexafluoropropylene) (PVDF-HFP) polymer has received a great attention as an alternative to the commercial separator in energy devices. Therefore, a ternary hybrid membrane PVDF-HFP/polyaniline (PANI)/graphene oxide (GO) (10 wt%, 25 wt%, and 40 wt%) was synthesized and characterized as a polymer electrolyte membrane (PEM) for lithium ion battery. The thermogravimetric (TGA) analysis and mechanical strength tests have carried out to see the potential of GO in alteration of mechanical and thermal properties of PVDF-HFP membrane; additionally, the scanning electron microscopy (SEM), x-ray diffraction (XRD), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), electrochemical stability, porosity, and electrolyte uptake have also performed to investigate the effect of GO addition on the performance of PVDF-HFP polymer matrix. The PVDF-HFP/PANI membrane has resulted in highest ionic conductivity of 1.04 × 10−3 mS cm−1, whereas, the GO addition has remarkably enhanced the reduced tensile strength of PVDF-HFP/PANI membrane from 2.8 MPa to 8.8 MPa. In addition, the presence of GO has found more impressive and resulted in the highest porosity of 89.5% and an excellent electrolyte uptake of 367.4% with PVDF-HFP/PANI/GO ternary PEM. Therefore, the proposed PVDF-HFP/PANI/GO ternary hybrid membrane can be applied as PEM or a separator in energy devices.