A series of acrylamide/dimethylaminoethylacrylate methyl chloride copolymers (AM-co-DMAEA) was evaluated as flocculants for model Precipitated Calcium Carbonate (FCC) in distilled water. These cationic polyelectrolytes (PEL) differed by their AM/DMAEA ratio, i.e., their charge density, chain architecture (linear and branched), their intrinsic viscosity (IV), and zeta potential of their aqueous solutions. The IV being directly related to the hydrodynamic volume of the PEL and the zeta potential reflecting the effective charges in suspension were selected for practically useful correlations with flocculation performance. The fractal dimension (d(F)) and the scattering exponent (SE) of the flocs, analyzed by the laser diffraction method, were taken as indication of primary particle and aggregate assembly. For the optimum PEL dosage, SE and d(F) varied with the IV and zeta potential. It was observable that floc size, floc resistance, and floc reorganization correlate with the PEL characteristics. Copolymers with lower IV, which is here associated with PEL of similar molar mass but lower charge density, yielded larger and less resistant flocs. Copolymers with higher IV originated smaller more compact flocs being more resistant. in high shear situations, where floc breakage should be avoided, as it is the case in papermaking, polymers with high IV yielding large SE are advantageous. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 3603-3612,2010