Based on aromatic diisocyanate [e.g., 2,4-tolylene diisocyanate (TDI)], a novel synthetic strategy to waterborne polyurethanes was introduced. Ionized polyoxyethylated amine (NPEO) played an important role in the preparation process as both a polyether soft segment and an internal emulsifier. First, a segmented surfactant prepolymer was synthesized. Second, the prepolymer was charged to a water dispersion of a hydrophobic polyol [e.g., polytetrahydrofuran (PTMO)] directly to obtain a stable emulsion. Third, a chain-extension procedure was performed directly in water with PTMO to achieve a stable aqueous polyurethane dispersion. Neither aliphatic diisocyanate nor excess isocyanate group fraction was added. An extra end-capping reaction or external emulsifier was also unnecessary. Films cast from emulsions exhibited reasonable mechanical properties.