The effect of cationic and anionic surfactants, as well as cationic and anionic polyelectrolytes (PE), their binary mixtures on the electrokinetic potential of monodisperse carboxylated polystyrene (PS) particles as a function of the reagents dose, pH, the charge density (CD) of polymers, the surfactant/PE and binary PE mixture composition, and sequence of components addition to the suspension has been studied. It has been shown that addition of increasing amount of anionic surfactant/polyelectrolytes increases the abso lute value of the negative zeta potential of PS particles; this increase is stronger the CD of the PE and pH of the system are higher. Adsorption of cationic surfactant/polyelectrolytes leads to a significant decrease in the negative ζ potential and to overcharging the particles; changes in the ζ potential are more pronounced for PE samples with higher CD and for suspensions with lower pH values. In mixtures of cationic and anionic PE, in a wide range of mixture composition, the ζ potential of particles is determined by the adsorbed amount of the anionic polymer independently of the CD of PEs and the sequence of addition of the mixture components. The isoelectric point of the surface is reached at the adsorbed amount of positive charges of PE that is approximately equal to the surface CD of particles. The laws observed were explained by features of macromolecules conformation in adsorbed mixed PE layers. Considerations about the role of coulombic and non coulombic forces in the mechanism of anionic/cationic PE adsorption are presented.