For many industrial applications, an extensive research of the stabilization and destabilization mechanisms of aqueous suspensions of fine particles is crucial. The flocculation of charged particles from their aqueous suspensions is greatly influenced by the surface characteristics of the particles. For the purpose of improving the flocculation efficiency of kaolin suspensions, the impact of the proposed mechanochemical treatment, which includes homogenization and/or ultrasonication followed by the addition of polycation such as poly (diallyl dimethyl‐ammonium chloride) (PDADMAC), was examined under standard conditions. It was demonstrated that parameters including kaolin's specific surface area, surface charge density, and particle size reduction are all affected by the duration of the ultrasonication. While ultrasonication (10 min) has a significant impact on particle size distributions, 300 and 200 nm‐sized particles were also seen. A narrow flocculation window was obtained by PDADMAC at a Cp/Cs ratio of 0.1 mg/g (Cp/Cs means the ratio of mass polymer/mass substrate), while the mechanical treatment via homogenization with magnetic stirring (60 min) resulted in a larger flocculation window of kaolin caused by the polyelectrolyte used. However, mechanochemical treatment via ultrasonication followed by the addition of aforementioned polyelectrolyte played a significant role in achieving the highest turbidity removal. Hence, the settling behavior of kaolin suspension depends upon the pH, ultra‐sonication time, and the concentration of polyelectrolyte. The combination of ultra‐sonication, PDADMAC dosage, and pH (mechanic‐chemical treatment) played an excellent role in the maximum removal of turbidity, and the broadest flocculation window comprising of 0.4 to 1.6 mg/g was observed at pH 8.