Acrylamide and 2-(methacryloyloxy)ethyl-trimethylammonium chloride (AM/MADQUAT) copolymers were synthesized by solution and inverse microemulsion polymerization using (NH4)(2)S2O8/NaHSO3 as redox initiator at the same feed mote ratio, and their microstructure, Such as sequence distribution and composition distribution, was calculated from monomer reactivity ratios of different polymerization methods. The results show that charge distribution is more uniform for copolymer prepared in inverse microemulsion than that in solution, and copolymer composition distribution is close to unity, and maintains approximately at the feed ratio. Furthermore, the influence of the two structures of cationic polyacrylamides on kaolinite floc size and effective floc density, reduction of Zeta potential and floc compressive yield stress had been investigated at pH 7. The results show that the kaolinite floc size and effective floc density are strongly dependent upon copolymer microstructure, with greater floc size and lower effective floc density being observed for copolymer prepared in inverse microemulsion than for that in solution. Copolymer microstructure has a marked effect on the Zeta potential, whose reduction in the magnitude was much greater in the presence of copolymer prepared in inverse microemulsion than that in solution. Greater compressive yield stress was achieved for the strong flocs produced by copolymer prepared in inverse microemulsion than for the weak flocs produced by that in solution. The difference in flocs compressive yield stress may be attributed to flocs structure. Therefore, in this article, a correlation between the cationic polyacrylamide structure and flocculation property for kaolinite Suspension was established. (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 110: 3889-3896, 2008