A hyperbranched (methacrylated poly(amine ester) (HPAE-2-A) was synthesized by the modification of the hydroxyl end groups of the second generation of a hyperbranched poly(amine ester) with acryloyl chloride and methacrylic anhydride. The photopolymerization kinetics were investigated with photo-differential scanning calorimetry and Fourier transform infrared. The properties of HPAE-2-A, including the dynamic viscosity, pendulum hardness, and shrinkage, were also studied in comparison with those of a hyperbranched methacrylated poly(amine ester) (HPAE-2-MA) prepared in the laboratory and traditional epoxy acrylate and epoxy methacrylate. HPAE-2-A polymerized rapidly under UV irradiation in the presence of a photoinitiator and had a higher final conversion of double bonds. The thermomechanical properties of UV-cured HPAE-2-MA films were compared with those of EB-cured films measured with a dynamic mechanical thermal analyzer.