Waterborne polyurethane was prepared by terminal-hydroxypolybutadiene (HTPB) and poly (neopentyl glycol adipate) (PNA) as soft segments. The structure of as-prepared waterborne polyurethane was characterized by FTIR, XRD and SEM. The mechanical performance of the polyurethane was investigated by peel strength test on the biaxially oriented polypropylene (BOPP) film. The results show that the particle size of the emulsion gradually increased with the molar content of HTPB increased. The surface energy gradually decreased, then kept stable with the molar content of HTPB increased. The best comprehensive performance of the polyurethane was obtained when the molar content of HTPB was 30% of PNA. The average particle size of the polyurethane emulsion was 287.3 nm and the surface energy of the film was 31.77 mJ/m2. The tensile strength of the film was 14.2 MPa and the elongation at break was 977.72%. The peel strength of the polyurethane on the BOPP film was 4.4 N/25mm.