Up to date, an increasing number of carbon-based nanomaterials have provided routes for the fabrication of smart and high-performance analytical microsystems. Graphene oxide (GO) as one promising carbon-based material has aroused much interest due to the moderate GO water dispersibility and reactive sites for further modification. In this study, free-standing laminar GO membrane was obtained on the tip of glass nanopipette by electrophoresis. Scanning electron microscope (SEM), optimal microscope and electrochemical method were used to determine the assembly process, respectively. Stable and obvious rectification change shows that gas molecule can modulate ion migration owing to the change of charge density between GO sheets. Such results may pave the way for development of gas differentiation membrane, and study on fundamental mechanism.