UV curing technology has become an efficient method to fabricate films with desirable properties, although it is susceptible to oxygen inhibition, resulting in low conversion of double bonds and poor mechanical performance. Thiol–ene click reaction can overcome the shortcomings of common UV curing techniques. In this paper, the vinyl-terminated hyperbranched polyester (VTDP) was incorporated into the curing system of di-ene (A2) and trithiol (B3). Trithiols, including 1,3,5-tris(2-hydroxyethyl)isocyanurate tris(3-mercaptopropionate) (THMP) and trimethylolpropane tris(3-mercaptopropionate) (TMMP), were synthesized by an esterification between 3-mercaptopropionic acid and 1,3,5-tris(2-hydroxyethyl) isocyanurate, and tri(hydroxymethyl)propane, respectively. The UV-initiated thiol–ene click reaction between 1,4-butanediol diacrylate (BDDA) and trithiols (TMMP and THMP) was researched by adjusting different VTDP content. FTIR spectral analysis showed that the thiol–ene reactions proceeded smoothly and the conversion degree of acrylic groups was higher than that of thiol groups. The pencil hardness and abrasion resistance of the cured film increased first and then decreased with the increase in VTDP content, but both their flexibility and adhesion had little change. Their glass transition temperatures increased slightly with the increase in VTDP content. THMP has better positive effect than TMMP on the pencil hardness, abrasion resistance and thermal performance of the cured film.