Polyelectrolyte microcapsules are used in the development of new forms of targeted delivery systems, self-healing materials, sensors, and smart materials. Nevertheless, their buffer capacity has not been practically studied, although that characteristic makes it possible to estimate the change in the state of protonation of the entire polyelectrolyte system. This is necessary both for creating a buffer barrier system for pH-sensitive compounds (metals, enzymes, polyelectrolytes, drugs) and for the correct interpretation of the results of research and studying of the PMC structure. The buffer capacity of a PMC can be affected by the concentration of microcapsules in solution and the number of shell layers since the listed parameters affect other physicochemical properties of the PMC shell. This includes, for example, the electrical conductivity, permeability (of ions), osmotic pressure, charge density, etc. In this regard, we studied the change in the buffer capacity of polyelectrolyte microcapsules depending on their concentration and the number of shell layers. As a result, it was found that with an increasing concentration of microcapsules, the buffering capacity of the PMC increases, but at the same time, in the pH range from 4 to 5.5, the calculated buffering capacity of 1 billion capsules decreases with increasing their concentration. This effect may be associated with a decrease in the available -NH2 groups of the PMC’s shell. In addition, it was found that the main contribution to the buffer capacity of a PMC is made by the entire shell of the microcapsule and not just its surface. At the same time, the buffer capacity of the capsules has non-linear growth with an increase in the number of PMC shell layers. It is presumably associated either with a decrease in the polyelectrolyte layer with an increase in their number or with a decrease in the permeability of hydrogen protons.