Interparticle forces and colloidal stability of aqueous clay mineral dispersions play an important role in many unit operations (e.g. crystallization, leaching and dewatering) and production processes. In this study, the effect of pulp chemistry on interparticle forces in concentrated aqueous muscovite dispersions have been investigated at 25 °C. Theoretical DLVO estimations of the total interaction forces and energy potentials between muscovite particles in the pH range 3–9 are made and reconciled with dispersion shear yield stresses and measured particle zeta potentials. Calculations made as a function of pulp chemistry indicate that a considerable reduction in energy barrier (from 3000 to 300 kT) and deeper secondary minimums at shorter separation distances may be achieved by decreasing pH from 9 to 6, where the magnitude of the particle zeta potential decreases markedly. It is also predicted that both the energy barrier to coagulation and secondary minimum disappear around the isoelectric point of muscovite particles (pH 4–5) where electrical double layer repulsive forces are eliminated. At pH 7, systematic reduction and disappearance of the interaction potential energy barrier with increasing ionic strength is predicted. The particle interaction energies estimated from shear yield stress measurements of concentrated aqueous muscovite dispersions as a function of pH and ionic strength show good agreement with the theoretical calculations, suggesting the dominance of DLVO forces in all conditions studied. The findings enable us to accurately rationalize the nature of interaction forces underpinning particle network structure and strength during aqueous processing of clay-based mineral dispersions.