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Magnesium hydroxide is commonly used as a coagulant for treating reactive dyes wastewater. However, the flocs are relatively small and coagulation process needs longer sedimentation time. Large flocs and short operation time are important for good coagulation performance. Coagulation floc formation and growth processes using magnesium hydroxide and polyacrylamide (PAM) dual-coagulant were investigated with controlled experiments through flocculation index (FI), floc size distribution, zeta potential, scanning electron microscopy and Fourier transform infrared spectroscopy. The final average floc size reached 58.5 and 4.96 μm with and absence of PAM addition during slow mixing periods. PAM feeding time and magnesium hydroxide formation time can affect the floc formation and growth processes. The results showed that floc formed rapidly during magnesium hydroxide generation within 90 s and flocs aggregated together by PAM bridging function. Reactive orange removal efficiency reached 99.3% with rapid mixing 250 rpm at 90 s during 100 mg/L magnesium ion addition, then adding 6 mg/L PAM at the beginning of slow mixing period in dual-coagulant system.