Nanocomposites play a key role in performance improvements of hydroxide conductors employed in a wide range of alkaline-electrochemical systems such as fuel cells and metal-air batteries. Graphene oxide (GO) nanosheets are considered to be outstanding nanofillers for polymeric nanocomposites on account of their excellent physicochemical strength and electrochemical properties. In this work, a fast hydroxide conductor was developed on the basis of a chemically modified GO nanocomposite membrane. The high surface area of GO was functionalized with highly stable hydroxide-conductive groups using a dimethyloctadecyl [3-(trimethoxysilyl)propyl]ammonium chloride (DMAOP) precursor, named QAFGO, and then composed with porous polybenzimidazole PBI (pPBI) as a well-suited polymeric backbone. The nanocomposite exhibited outstanding hydroxide conductivity of 0.085 S cm(-1), high physicochemical strength, and electrochemical stability for 21 days. An alkaline fuel cell (AFC) setup was fabricated to determine the functionality of QAFGO/pPBI nanocomposite in an alkaline-based system. The high AFC performance with peak power density of 86.68 mW cm(-2) demonstrated that QAFGO/pPBI nanocomposite membrane has promising potential to be employed as a reliable hydroxide conductor for electrochemical systems working in alkaline conditions.