Vanillin/fluorosilicone-modified waterborne polyurethane emulsion is prepared by stepwise polymerization using hydroxy silicone oil, perfluorooctanol and vanillin as modified monomers, and is applied to finishing of hemp fabric. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirm the successful grafting of fluorosilicon chain segments and vanillin. Scanning electron microscopy observation shows that a uniform and dense protective film is formed on the fiber surface. The performance test results show that the water contact angle of the finished fabric reaches 141.44°, showing excellent hydrophobicity. The antibacterial test shows that the inhibition rate of Escherichia. coli and Staphylococcus aureus are 98.9% and 99.9%, respectively. At the same time, the breaking strength and breaking elongation are improved, and the finished hemp fabric has good UV resistance and stain resistance.