HEREIN, two polyurethane oligomers were successfully synthesized using a prepolymer mixing process. The prepolymers were synthesized based on the step-growth addition polymerization of polypropylene glycol, Methylene diphenyl diisocyanate and 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate. Isopropanol was functioned as the isocyanate blocking agent. Thereafter, different terpolymer emulsions were prepared by the emulsion graft copolymerization with the vinyl acetate monomer in presence of 2-ethylhexyl acrylate as a vinyl monomer. The chemical structures of the synthesized oligomeric monomers were probed by FTIR spectroscopy and found to vary with the content of acrylic monomer used in the oligomer synthesis phase (i.e.hydroxyethyl acrylate or hydroxyethyl methacrylate). The topography, thermal stability, and particle size of terpolymers were investigated by SEM, TGA, and zeta potential, respectively. The TGA results demonstrated marked enhancement in thermal stability of the synthesized terpolymers up to ca. 600°C, which was concurrent with enhanced surface homogeneity and film properties as evidenced by the SEM images. These terpolymers showed also property enhancement as binders for textile pigment printing in terms of rubbing resistance, color strength and fastness to washing when compared to the commercial binders. These judgments would provide a new competent synthesis route by introducing polyurethane acetate vinyl acrylate as the binder for use in pigment printing of cotton fabrics.