This study evaluated the combined effect of a cationic coagulant (Magnafloc 1727^®) and a high molecular weight anionic flocculant (SNF 604^®) on the settling properties, aggregate structure, and rheological behavior of synthetic tailings suspensions composed of kaolinite and quartz in industrial water at pH 11. Settling tests, focused beam reflectance measurement (FBRM), zeta potential measurement, and rheological characterization were used to analyze the system’s performance under different coagulant dosages (0–150 g/t), while keeping the flocculant dosage constant (20 g/t). The results indicated that the coagulant favored surface charge neutralization, shifting the zeta potential from −13.2 mV to +4.0 mV. This resulted in larger, more efficient flocs capturing fines, with a 46% turbidity reduction. FBRM analysis revealed a significant increase in aggregate size and a slight decrease in fractal dimension (from 2.35 to 2.20), consistent with larger volume structures and lower bulk density. Rheologically, a substantial increase in yield stress was observed, especially in 50 wt% suspensions, suggesting the development of a continuous flocculated network with greater mechanical strength. These findings highlight the importance of sequential chemical conditioning in clayey tailings and its impact on clarification efficiency and water recovery under alkaline conditions representative of industrial mining processes.