AbstractThe bio‐based hydrophilic monoglycerol succinate was synthesized and reacted with bio‐based raw materials including polyols, pentamethylene diisocyanate, 1,4‐butanediol, to prepare the waterborne polyurethane acrylate (Bio‐WPUA) emulsions with high bio‐based content. The effect of bio‐based polyol categories including poly(trimethylene ether glycol), poly(tetrahydrofuran), and castor oil on the properties of Bio‐WPUA and its films were studied. The structure, thermal stability, crystallinity, contact angle, and mechanical properties of Bio‐WPUA film were characterized with fourier infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, X‐ray diffraction, contact angle analyzer, and mechanical tensile testing. It was found that Bio‐WPUA film containing poly(trimethylene ether glycol) as the soft‐segmented display good tensile stress, thermal stability, and water resistance with 1.38% of the water absorption rate, while Bio‐WPUA containing castor oil polyol as the soft‐segmented had good tensile strain and low‐temperature film‐forming properties with excellent film properties. The bio‐carbon content of Bio‐WPUA was high up to 40% according to ASTM D6866‐22, and possesses good physical mechanical and chemical resistance performance. The results provide theoretical guidance for the synthesis of polyurethane emulsions with bio‐based materials instead of petroleum‐based materials.