In nanometer-sized apertures with charged surfaces, the extension of the electrical double layer results in the electrostatic exclusion of co-ions and enrichment in counterions, which affects the permselectivity of such structures. A modeling of this phenomenon is proposed and is compared with quantitative measurements of the ionic permeability change of a Pyrex nanoslit at low ionic strength. The comparison of experimental results with theoretical predictions justifies that electrostatic forces are the governing forces in nanofluidics.