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An ionomer-type of polyurethane (PU) emul-sion was prepared from toluene diisocyanate (TDI), polypropylene glycol (PPG) and dimethylol propionic acid (DMPA) following a self-emulsification process. The modified poly(vinyl chloride) (PVC) emulsion resin was obtained by in situ emulsion copolymerization using the PU as seeds in an autoclave. The effects of PU molecular weight on the mechanical properties and thermal stability of the PU/PVC materials were investigated. The composite latex particles and composite materials were determined and characterized using a laser particle size analyzer, transmission electron microscopy or scanning electron microscopy. The study results showed that the PU/PVC hybrid emulsion particles possess a core/shell structure. When the general mechanical properties of the composite materials increase, the thermal stabilities decrease a little. The tough fractures on the surface of the PU/PVC composite sample following impact are quite obvious.