Cation transport through nanochannels in graphene oxide can be rectified to give ionic diode devices for future applications, for example, in desalination. A film of graphene oxide is applied to a 6 μm thick poly(ethylene terephthalate) substrate with a 20 μm diameter microhole and immersed in aqueous HCl solution. Strong diode effects are observed even at high ionic strength (0.5 M). Switching between open and closed states, microhole size effects, and time-dependent phenomena are explained on the basis of a simplified theoretical model focusing on the field-driven transport within the microhole region. In aqueous NaCl, competition between Na+ transport and field-driven heterolytic water splitting is observed but shown to be significant only at low ionic strength. Therefore, nanostructured graphene oxide is demonstrated to exhibit close to ideal behavior for future application in ionic diode desalination of seawater.