Our work has focused on the development of polymer electrolyte materials, and the membranes for the potential application of AEMFC, PEMFC, redox flow battery, and other electrochemical energy fields. Alkaline anion exchange membrane fuel cells (AEMFCs) attract much attension because they could utilize non-noble metals as catalysts, such as Ni, Ag etc instead of noble platinum catalysts in PEMFC, and exhibited enhanced oxygen reduction kinetics. A high molecular weight polybenzimidazole (PBI) with side chain ammonium cations was synthesized, and the anionic exchange membranes (AEM) with high OH- conductivity was obtained. The other properties of IEC, water-uptake, swelling ratio, and the stability were investigated systematically. Then, a hyperbranched poly(ether ketone) HB-PEK/CMPPEK based composite alkaline membrane (BAEM) were prepared in order to obtain the low swelling AEM materials. The chemical structure of BAEMs was characterized by FT-IR and 1H-NMR, respectively. The physicochemical properties such as the IEC, swelling ratio, water uptake, OH^- conductivity and mechanical properties of the BAEM membranes were examined. Last, sulfonated graphene oxides (SSi-GO) were synthesized by grafting 3-mercaptopropyl trimethoxysilane (MTPS) with graphene oxide (GO) and follow-up oxidation of hydrogen peroxide. Furthur, SSi-GO based composite membranes was prepared with SPPEK aimed at the establishment of the ionic transport channel. The proton conductivity of 10% content composite membranes reached 0.094 S/cm at 30℃, and 0.220 S/cm at 80℃ much higher than Nafion 117, which indicated the potential application of SPPEK-SSi-GO composite membranes for PEMFC.