Hydroxyl surface density in porous silica drops down to nearly zero when the pH of the confined aqueous solution is greater than 10.5. To study such extreme conditions, we developed a model of slit silicananopores where all the hydrogen atoms of the hydroxylated surface are removed and the negative charge of the resulting oxygen dangling bonds is compensated by Ca²⁺ counterions. We employed grand canonical Monte Carlo and molecular dynamics simulations to address how the Ca²⁺ counterions affect the thermodynamics, structure, and dynamics of confined water. While most of the Ca²⁺ counterions arrange themselves according to the so-called “Stern layer,” no diffuse layer is observed. The presence of Ca²⁺ counterions affects the pore filling for strong confinement where the surfaceeffects are large. At full loading, no significant changes are observed in the layering of the first two adsorbed water layers compared to nanopores with fully hydroxylated surfaces. However, the water structure and water orientational ordering with respect to the surface is much more disturbed. Due to the super hydrophilicity of the Ca²⁺-silica nanopores,waterdynamics is slowed down and vicinal water molecules stick to the pore surface over longer times than in the case of hydroxylated silicasurfaces. These findings, which suggest the breakdown of the linear Poisson–Boltzmann theory, provide important information about the properties of nanoconfined electrolytes upon extreme conditions where the surface charge and ion concentration are large.