Multifunctional polyurethane acrylates were synthesized by two-step process. The photopolymerization kinetics of multifunctional polyurethane acrylates was monitored by real-time FTIR. The mechanical properties of multifunctional polyurethane acrylates in comparison with other monomers formulation were also studied. The results showed that, the structure of polyurethane acrylates had great effect on the conversion of double bond. It meant the more the functionality of polyurethane acrylates, the lower the double bonds converted. The hardness of coating film was improved with the increase of functionality of polyurethane acrylates.