Interfacial charge in a solid/liquid system is due to interactions of ions with surface sites affected by the electrostatic potential that is a consequence of their accumulation. The present theoretical approach is based on the so-called Surface Complexation Model that has several modifications known as either the 1-pK, the 2-pK, or the "MUSIC" model. These models assume different surface reactions and their equilibrium constants, taking into account electrostatic interactions. For that purpose the relationships between potentials affecting the state of interfacial ions and their surface densities need to be known, so that a certain model of the electrical interfacial layer should be introduced. The complexity of the problem results in the use of a variety of different theoretical approaches that cannot be distinguished experimentally. This article discusses several aspects of the problem, such as counterion association, structure of the electrical interfacial layer, potential-charge relationships, surface potentials, the zero charge condition, enthalpy of surface reactions, and the influence of the interfacial ionic equilibrium on the colloid stability.