The formation of the electrical double layer (EDL) in an aqueous solution in contact with the charged solid surfaces of a slit-type nanopore has been simulated by grand canonical Monte Carlo (GCMC) and canonical Monte Carlo (CMC) methods. In the GCMC simulations, a primitive EDL model in which water is considered as a continuum and the ions are considered as hard spheres is used. The results are found to be slightly different from those predicted by the Gouy-Chapman model at low electrolyte concentration and low surface charge density. The GCMC results were then used as an initial condition for the CMC simulations of a nonprimitive model in which the EDL is composed of molecular water (four-point transferable intermolecular potential, together with fluctuating charge model), cations (Na+), and anions (Cl-). The nonprimitive model provides a very different view of the EDL at the atomic level. For example, a single layer of water molecules, instead of counterions, is strongly adsorbed on negatively charged surfaces. This feature cannot be observed in the Gouy-Chapman or in the primitive model. Moreover, because the charged surfaces are covered by water molecules, the maximum counterion concentration in a nanopore occurs at the center, instead of on the surfaces, of the pore. This phenomenon is also supported by experimental data and theoretical calculations found in the literature.