Disulfide-containing coatings are gaining importance due to the peculiar properties and responsiveness of SS bonds, which make them suitable for several applications, first among themself-healable materials. Herein, a novel UV-curable diacrylated polyurethane monomer containing disulfide bonds (DSPDA) was synthesized through a one-step process without the need for further purification, as assessed by NMR and HPLC analyses. The photopolymerization kinetics of the monomer was studied through real-time FTIR, highlighting a fast and complete conversion even in the absence of a photoinitiator, thus demonstrating the self-initiating capabilities of the synthesized monomer based on the disulfide cleavage upon UV light exposure. Clear coatings having a Tg = 72 °C were obtained. The self-healing ability of the films was assessed: thanks to the presence of disulfide bonds in the cured coating, a recovery of the damage was obtained in only 10 min by heating at 100 °C.