Firstly, the monomer of N, N-diethylol-3-amine methylpropionate was obtained via Michael addition of methyl acrylate and diethanolamine. Then the hyperbranched poly (amine-ester) (HBPE) was synthesized through pentaerythritol as core molecules and monomer as AB(2). HBPE was characterized by Fourier transform-infrared spectroscopy, hydrogen nuclear magnetic resonance (H-1-NMR) and elemental analysis. Methyl tetrahydrophthalic anhydride (MTHPA) is grafted to the hydroxyl groups of HBPE and then glycidyl methacrylate (GMA) is introduced to the structure of HBPE, which is obtained by the UV-curable hyperbranched prepolymer (HBPE-MTHPA-GMA). Ultraviolet-differential scanning calorimeter showed that the HBPE-MTHPA-GMA has high photocuring speed under photoinitiator. Furthermore, the films also show good impact strength, outstanding adhesive force and primary thermal stability.