In polyelectrolyte-enhanced ultrafiltration (PEUFF), a cationic polyelectrolyte binds to chromate and is ultrafiltered from solution. The permeate passing through the membrane can contain a very low chromate concentration, the retentate solution not passing through the membrane must be treated to recover a large fraction of the polymer for reuse for economical operation, In the regeneration step, barium chloride can be added to the retentate to precipitate chromate anion as a compact barium chromate solid waste. The solution containing the polymer can be directly recycled after the solid barium chromate is separated from the solution. Gravity settling is much less expensive than filtration or centrifugation, so this investigation studies the ability to separate solid from solution in a settling unit. Unfortunately, the polyelectrolyte can act as a dispersing agent that stabilizes the dispersion of barium chromate particles, resulting in poor separation efficiency in the settler. The adsorption of cationic polyelectrolyte on barium chromate particles increases with increasing polymer concentration, increasing ionic strength, and decreasing barium-to-chromate ratio. In addition, adsorption of the polyelectrolyte onto the barium chromate particles inhibits the growth of crystals and affects the crystal morphology. The average particle size of barium chromate crystals formed in the presence of the polymer is less than in the absence of the polymer, As a consequence, slower settling of the smaller particles occurs in the presence of polymer. The sedimentation rate of barium chromate increases with decreasing polymer concentration, increasing temperature, and increasing electrolyte concentration and reaches a maximum when there is a stoichiometric ratio of barium to chromate present. At this stoichiometric ratio in the absence of polymer, the zeta potential is zero, confirming that the rapid settling is due to the absence of electrostatic repulsion between the particles. Even though the barium chromate settles rapidly in the absence of polymer, the polymer adsorbs on the crystals and acts like a dispersant as well as causing a solution viscosity increase, resulting in slow settling rates in the PEUF process where the polyelectrolyte must be present.