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Waterborne polyurethane (WBPU)/cerium nitrate (Ce(NO₃)₃) dispersions were synthesized with different defined Ce(NO₃)₃ content. All pristine dispersions were stable with different poly(tetramethylene oxide) glycol (PTMG) number average molecular weights (M_n) of 650, 1000, and 2000. The interaction between the carboxyl acid salt group and Ce(NO₃)₃ was analyzed by Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) techniques. Coating hydrophilicity, water swelling (%), water contact angle, leaching, and corrosion protection efficiency were all affected when using different Ce(NO₃)₃ content and PTMG molecular weights. The maximal corrosion protection of the WBPU coating was recorded using a higher molecular weight of PTMG with 0.016 mole Ce(NO₃)₃ content.