Thiolactone chemistry is a powerful tool for the design of complex multifunctional architectures. In this study, this versatile click-inspired synthetic strategy is conducted to prepare multifunctional dendrimer-like structures. For this purpose, a thiolactone bearing an isocyanate function, prepared in multigram scale, is utilized for multiple step functionalization starting from a 4-arm star-shaped poly(ethylene glycol). Amine-thiol-acrylate conjugation is carried out in order to form the aforementioned structures. The efficient aminolysis of the thiolactone ring and the reaction of the generated thiol with the double bond of an acrylate derivative are completed in a one-pot procedure. The choice of the amine and/or acrylate derivatives can allow the introduction of different functional groups for each new gene-ration, potentially leading to multivalent dendrimer-like structures.