This study explores the synthesis and evaluation of UV-curable urethane (meth)acrylates (UA) incorporating a Diels–Alder adduct (HODA), diisocyanate, poly(ethylene glycol), and hydroxy (meth)acrylate. Six UAs, distinguished by the soft segment of polymer chains, underwent comprehensive characterization using FTIR and NMR spectroscopy. Real-time monitoring of the UV-curing process and analysis of self-healing properties were performed. The research investigates the influence of various molecular weights of PEGs on the self-healing process, revealing dependencies on photopolymerization kinetics, microstructure, thermal properties, and thermoreversibility of urethane (meth)acrylates. This work provides valuable insights into the development of UV-curable coatings with tailored properties for potential applications in advanced materials.