The KCl/PHPA waste drilling fluid is produced during drilling operations in Bohai Oilfield, China, which cannot be directly used or discharged, it needs to be flocculated. In order to know the aggregation mechanism of colloidal particles in KCl/PHPA drilling fluid, the calculation method of zeta potential and the relationship between the stability of waste fluid and zeta potential are discussed in detail in this article. The process of decreasing the zeta potential of waste fluid due to the addition of cationic polyacrylamide is called instability. The process in which unstable particles aggregate into larger particles is called coagulation, and the process in which unstable particles aggregate into large flocs is called flocculation. According to the types of treatment agents in KCl/PHPA waste drilling fluid, the structure and energy changes formed between low-viscosity polyanionic cellulose, partially hydrolyzed polyacrylamide, xanthan gum, starch, and water molecules are constructed. The energy of the four treatment agent systems decreased by 21.4–67.5% after the cationic polyacrylamide was added. The reduction of system energy reduced the repulsive force between colloidal particles in the waste fluid and promoted the agglomeration of colloidal particles. The agglomeration mechanism of waste liquid particles was obtained.