Magnesium hydroxide was used as a coagulant for treating reactive orange wastewater in a real continuous process. Effects of kaolin on coagulation performance and floc properties were investigated with controlled experiments through floc size distribution, zeta potential, scanning electron microscopy and Fourier transform infrared spectroscopy. Kaolin had significant influence on magnesium hydroxide-reactive orange floc formation and growth. The results showed that average floc size reached 16.31, 12.88 and 20.50 μm, respectively, in the rapid mixer, flocculation basin and sedimentation tank when kaolin concentration was 10 mg/L and reactive orange initial concentration was 0.25 g/L. The floc size tended to increase with the increase of kaolin suspension to 10 mg/L. All of the flocs under investigation showed that floc breakage led to decreased average floc size and remained stable in the flocculation basin. Reactive orange and kaolin could be removed effectively in the continuous coagulation process. Reactive orange was adsorbed in the surface of magnesium hydroxide through charge neutralization and adsorption.