Poly(allylamine) hydrochloride is a weak cationic polyelectrolyte that exhibits different aggregation properties at different solution pH values and aging times. Specifically, after several days aging in a pH 3 buffer, less than 1 mg/mL poly(allylamine) hydrochloride became turbid, and the hydrodynamic radius increased with a single diffusion mode. However, the hydrodynamic radius did not change at high concentrations. The dynamic processes of polymer aggregations at different pH values were verified by a light scattering and zeta-potential apparatus. The major interaction was caused by the capturing of counterions by the polyelectrolyte, which generates electrostatic, hydrophobic and cation-p interactions.