This report introduces a novel UV-curing technology based on thiol-thiol coupling for polydisulfide network formation. Beginning with a model tris(3-mercaptopropionate) trithiol monomer and xanthone propionic acid-protected guanidine as photobase generator, a comprehensive characterization based on spectroscopic techniques supports the reaction of thiols into disulfides without side reactions. The best experimental conditions are described as regards to film thickness, irradiance, emission wavelength, and atmosphere composition. The results shed light on a step-growth photopolymerization mechanism involving two steps: first, the formation of thiyl radicals by thiolate air oxidation or/and thiol photolysis, and second, their recombination into disulfide. By varying thiol functionality and structure, oligomer chain length and monomer/oligomer ratio, the network architecture can be finely tuned. The molecular mobility of the polydisulfide network is crucial to high thiol conversion rates and yields as revealed by H-1 T-2 NMR relaxation measurements. Ultimately, spatial control enables the formation of a photopatterned poly(disulfide) film, used as next-generation high refractive index photoresist. (c) 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 117-128.