In order to evaluate the influence of particle size and particle concentration on the coagulation process, two kinds of particle suspensions, nanoparticles and microparticles, were employed to investigate the effect of particle size on coagulation mechanisms with varying coagulation parameters. Results showed that it is easier for nanoparticles to cause self-aggregation because of Brownian motion, while interception and sedimentation are the mainly physical processes affecting particle transport for microparticles, so they are more stable and disperse more easily. The particle size distribution and particle concentration had distinct influence on the coagulation mechanisms. Under neutral conditions, as the amount of coagulant increased, the coagulation mechanism for nanoparticles changed from charge neutralization to sweep flocculation and the nanoparticles became destabilized, re-stabilized and again destabilized. For microparticles, although the coagulation mechanism was the same as that of nanoparticles, the increased rate of aluminum hydroxide precipitation exceeded the adsorption of incipiently formed soluble alum species, resulting in the disappearance of the re-stabilization zone. Under acidic conditions, Brownian motion dominates for nanoparticles at low particle concentrations, while sweep flocculation is predominant at high particle concentrations. As for microparticles, charge neutralization and sweep flocculation are the mechanisms for low and high particle concentrations respectively. Under alkaline condition, although the mechanisms for both nano- and microparticles are the same, the morphology of flocs and the kinetics of floc formation are different. At low particle concentrations, nanoparticles have larger growth rate and final size of flocs, while at high particle concentrations, nanoparticles have higher fractal dimension and recovery factors.