Two-dimensional (2D) materials formed by thin-films of metal oxides that grow on metal supports are commonly used in heterogeneous catalysis and multilayer electronic devices. Despite extensive research on these systems, the effects of charged defects at supported oxides on surface processes are still not clear. In this work, we perform spin-polarized density-functional theory (DFT) calculations to investigate formation and interaction of charged magnesium and oxygen vacancies, and Al dopants on MgO(001)/Ag(001) surface. The results show a sizable interface compressive effect that decreases the metal work function as electrons are added on the MgO surface with a magnesium vacancy. This surface displays a larger formation energy in a water environment (O-rich condition) even with additional Al-doping. Under these conditions, we found that a polar molecule such as CO is more strongly adsorbed on the low-coordination oxygen sites due to a larger contribution of the channeled electronic transport with the silver interface regardless of the surface charge. Therefore, these findings elucidate how surface intrinsic vacancies can influence or contribute to charge transfer, which allows one to explore more specific reactions at different surface topologies for more efficient catalysts for CO2 conversion.