Floc structure plays an important role in the separation of coal wastewater. In this study, a camera-based method is used to evaluate quantitatively the structural characteristics of flocs generated by different coagulants and flocculants. The correlations between particle size, settlement velocity and effective density of coal tailings flocs are analysed. The results show that the statistical settling velocity increases linearly with floc size, while the effective density decreases with increase in floc size. Different flocculation mechanisms lead to diverse growth abilities of flocs. When the flocculant is used alone, the quality of the flocs generated by the flocculants, cationic polyacrylamide (CPAM) and non-ionic polyacrylamide (NPAM), is better than that generated by anionic polyacrylamide (APAM). However, the combination of trivalent cations and APAM yields a much better effect than that obtained using CPAM and NPAM. Flocs become larger and more compact when treated with a coagulant combined with a flocculant.