In the present study, a polyurethane acrylate (PUA) system cured via a thermal–UV (dual-cure process) was developed. The system selected for this work was a two-pack polyurethane acrylate with polyester polyol as the main component and urethane monoacrylate (UMA) as hardener. The polyester polyol was synthesized in a way to provide a final film coating containing both a suitable flexibility and high surface hardness. The thermal and photochemical curing behavior of the resin was studied via the chemorheology technique and the real-time FTIR. The Boltzmann sigmoidal model was implemented and well-fitted to the data obtained from the chemorheology measurements. The comparison between two reactive diluents, butanediol diacrylate (BDDA) and trimethylolpropane triacrylate (TMPTA) showed that BDDA reacts faster than TMPTA in the thermal curing condition. Nevertheless, the network buildup is stronger when TMPTA is used. The photopolymerization is also faster for the case of TMPTA. However, its final double bond conversion is restricted to a lower amount due to steric hindrance and higher viscosity of the system.