Crystals of lead sulfate were precipitated in solutions of various polyelectrolyte polymers (acidic, neutral, and basic polymers) using a double-jet crystallizer. Polyetyleneimine (PEI) basic polymer controlled both the nucleation rate and crystal growth rate, and enabled the production of fine monodispersed crystals. The on-line measurement of the variation in the lead concentration indicated that PEI lost its effect when a certain amount of the reactants N-tot was supplied. Interaction between lead ions and PEI was detected by NMR analysis, which suggested that lead ions made some kind of complex with PEI. The values of N-tot correlated well with the weight of PEI in the solution, regardless of the feed flow rate and reactant concentration, as shown in the correlative equation N-tot = k W-0.49. It was suggested that PEI could no longer control the precipitation rate when the amount of reactants supplied exceeded N-tot. Thereafter, rapid nucleation occurred. Precipitation with PEI could be controlled by a certain amount of PEI in a ground solution in order to produce monodispersed fine crystals. These results give an effective idea of how to create various nm size crystals.