Graphene oxide (GO) is a potential material in the electrode and membrane of polymer electrolyte membrane fuel cells due to its unique structure and various oxygen-containing functional groups. A class of three-layered GO/poly (phenylene oxide) for AEMs was prepared in this work. GO was functionalized with highly stable 6-azonia-spiro [5.5]undecane groups and used as a fast hydroxide conductor, named ASU-GO. Functionalized by N-spirocyclic cations, poly (phenylene oxide) (PIPPO) was then combined with ASU-GO and GO to fabricate the ASU-GO/ PIPPO and GO/PIPPO. Notably, the maximum hydroxide conductivity of the ASU-GO/PIPPO was 73.7 mS cm(-1) at 80 degrees C, which was 3 times higher than that of the GO/PIPPO. The enhancement in hydroxide conductivity was due to the changes in the hydroxide transport mechanism and the poor stacked structure of the ASU- GO layer. Only 10.8% drops in hydroxide conductivity of ASU-GP/PIPPO after the alkaline test (1 M KOH at 80 degrees C for 700 h). Furthermore, the ASU-GO/PIPPO-50 membrane showed a maximum peak power density of 102 mW cm(-2), demonstrating the prepared membrane was promising in the AEM applications. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.