We measured the proton conductivity of bulk graphite oxide (GO′), a graphene oxide/proton hybrid (GO-H), and a graphene oxide (GO) nanosheet for the first time. GO is a well-known electronic insulator, but for proton conduction we observed the reverse trend, as it exhibited superionic conductivity. The hydrophilic sites present in GO as −O–, −OH, and −COOH functional groups attract the protons, which propagate through hydrogen-bonding networks along the adsorbed water film. The proton conductivities of GO′ and GO-H at 100% humidity were 10–4 and 10–5 S cm–1, respectively, whereas that for GO was amazingly high, nearly 10–2 S cm–1. This finding indicates the possibility of GO-based perfect two-dimensional proton-conductive materials for applications in fuel cells, sensors, and so on.