High solid and high stability waterborne polyurethanes were molecularly designed and synthesized. The positions and concentrations of the anionic groups were varied, along with the molecular weights of the polyol. It was found that the dispersions containing ionic groups at the chain termini (called terminal ions) gave the smallest dispersion size, and the highest dispersion stability and viscosity, whereas the hard ions, containing ionic groups in the hard segments, resulted in the greatest swelling in water. However, the mechanical and dynamic mechanical properties of the dispersion cast films were similar. it was demonstrated that highly stable dispersions with a high solid content (45%) can be obtained at a low ionic content (2%) by simply incorporating the ionic groups at the flexible chain ends. The results were interpreted in terms of the high mobility and low free energy of the chain ends. (C) 2009 Elsevier Inc. All rights reserved