Despite enormous interest toward graphene oxide (GO) from the research community, surprisingly, little is known about its solutions. In particular, the questions related to the structure of the GO/liquid interface have not been yet properly addressed. In this report, we use a simple but efficient experimental approach to investigate the distribution of the four metal cations Na+, Cs+, Ni2+, and Gd3+ at the GO/water interface. We demonstrate that the concentration of the cations decreases exponentially with the distance from the GO surface. Such distribution for colloid systems was theoretically predicted and commonly accepted for a century but, to the best of our knowledge, has been never proved experimentally. We further demonstrate that the shape of the counterion distribution profiles depends on the pH of solution and on the fine chemical structure of GO. In particular, organic sulfates and vinylogous acids that are ionizable at different pH levels are responsible for the difference in the shapes of the concentration profiles. Unlike classical colloid systems, the diffuse layer in the GO solutions is rather broad (30-55 nm), and the concentration gradient is registered even at distances of >55 nm from the GO surface, which is typically considered as the bulk solution. The latter observation is explained by the immobilized character of the GO flakes in the nematic phase, impeding the flow of liquid and the migration of hydrated metal cations. This helps to establish and maintain the long-range concentration gradient in the space between the two parallel neighboring GO flakes. Based on the new findings and on the previously reported data, we formulate some basic principles of GO solutions.