Solution chemistry is commonly regarded as the physical chemistry of reactions and chemical equilibria taking place in the bulk of a solvent, and between solutes in solution, and solids or gases in contact with the solution. Our knowledge about such reactions and equilibria in aqueous solution is very detailed such as their physico–chemical constants at varying temperature, pressure, ionic medium and strength. In this paper the solution chemistry in the surface region of aqueous solutions, down to ca. 10 Å below the water–air interface, will be discussed. In this region, the density and relative permittivity are significantly smaller than in the aqueous bulk strongly affecting the chemical behaviour of solutes. Surface sensitive X-ray spectroscopic methods have recently been applicable on liquids and solutions by use of liquid jets. This allows the investigation of the speciation of compounds present in the water–air interface and the surface region, a region hardly studied before. Speciation studies show overwhelmingly that neutral molecules are accumulated in the surface region, while charged species are depleted from it. It has been shown that the equilibria between aqueous bulk, surface region, solids and/or air are very fast allowing effective transport of chemicals over the aqueous surface region.