The compatibility of polyorganylsiloxanes and high-molecular polymers used as emulsifiers was evaluated. The surface and bulk properties of the studied compounds were evaluated using the solubility parameters (δ). It is shown that the copolymers of acrylic acid compound – polyacrylamide and hydrolyzed polyacrylamide, as well as polyvinyl alcohol without residual acetate groups in the macromolecule have the highest degree of incompatibility with polyorganylsiloxanes. It was established that the presence of residual acetate groups in the macromolecule of polyvinyl alcohol leads to an increase in the degree of compatibility of polymers. The calculated data on the fractions of solubility parameters and cohesive energy of polyorganylsiloxanes and emulsifying polymers are presented. The contributions of the components of polymers cohesive energy due to the fractions of dispersion interaction αd, dipole-dipole interaction αdd, and hydrogen bonding αh, as well as their influence on the degree of solubility of the polymer – emulsifier system, are shown. The choice of polyvinyl alcohol with residual acetate groups as an emulsifier for polyorganylsiloxanes is theoretically substantiated based on the concept of the solubility parameter as a measure of the affinity of the system components. The developed approach to assessing the compatibility of the polymer – emulsifier system is of practical importance for the creation of polymer compositions in the finishing works.