Intrinsic cross-linked waterborne polyurethane (CWPU) was successfully synthesized for the first time through solvent-free condensation polymerization, in which green castor oil (CO) was used as the cross-linking agent. The totally solvent-free process was realized by using hydrophilic polypropylene glycol as hydrophilic segment, which was synthesized by the esterification of polypropylene glycol with pyromellitic dianhydride. The effect of CO content in the soft segment of the prepared CWPU on emulsion properties was investigated by laser particle size distribution test, and the prepared CWPU emulsion showed uniform size distribution (0.117-0.275 mu m) and milky white appearance after storing at ambient temperature for 6 month. Additionally, the effect of CO content in CWPU films on static mechanical properties, dynamic mechanical properties, hydrophilicity and thermal stability was also studied by tensile test, dynamic mechanical analysis, water absorption and contact angle measurement as well as thermogravimetric analysis. The prepared cross-linked CWPU films have good stability and outstanding mechanical strength (11.94-34.51 MPa), making them adequate supplement for the conventional waterborne polyurethanes.