Water electrolysis is an environment-friendly process of producing hydrogen with zero-carbon emission. Herein, we studied the water vapor electrolysis using a proton-conducting membrane composed of graphene oxide (GO) nanosheets intercalated with cations (Al3+ and Ce3+). We examined the effect of cation introduction on the physical and chemical structures, morphology, thermal and chemical stabilities, and the proton conductivity of stacked GO nanosheet membranes by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoemission spectroscopy (XPS), Raman spectroscopy, atomic force microscopy (AFM), dynamic light scattering (DLS), thermogravimetric-differential thermal analysis (TG-DTA), and electrochemical impedance spectroscopy (EIS). Concentration cell measurements revealed that the cation-modified membranes are pure proton conductors at room temperature. The proton conductivity of a GO membrane was much improved by cation modification. The cation-modified GO membranes, sandwiched with Pt/C electrodes as the cathode and anode, electrolyzed humidified air to produce hydrogen at room temperature, indicating the feasibility of this carbon-based electrochemical device.