The advanced anaerobic digestion process enhances sludge resource utilization. However, thermal hydrolysis pretreatment of anaerobically digested sludge reduces dewatering efficiency due to excessive organic matter decomposition. This necessitates significant time and effort for sludge conditioning in wastewater treatment plants. Using conditioning agents can achieve high dewatering efficiency. This study investigates how the order of adding coagulants and flocculants impacts the dewatering performance of digested sludge. The results indicate that, compared to the flocculation–coagulation process with the same dosage, the coagulation–flocculation process leads to a 15–20% increase in the average particle size of digested sludge. The content of polysaccharides and proteins in S-EPS decreases by 28.8–30.8% and 10.1–11.3%, respectively. The filter cake solids content increases by 8.5%, and there is an increase in surface water channels within the flocs. This is because initially adding coagulants efficiently adsorbs small particles, forming larger aggregates that settle effectively. This promotes the breakdown of extracellular polymeric substances, releasing more bound water. Adding flocculants later bridges the aggregates, further enhancing settling and filtration performance, thereby improving sludge dewatering efficiency. These research findings contribute to a better understanding of the mechanisms of coagulant and flocculant co-conditioning for digested sludge and provide recommendations for optimizing sludge conditioning steps.