An allyl terminated hyperbranched polyester (HBP) was added to an epoxy formulation containing a trithiol compound to perform a thiol-ene click reaction. By this procedure a flexible thioether network was formed. The photoirradiation of the reactive mixture, which contained a cationic photoinitiator, converted the thioether network in a multifunctional thermal macroinitiator, capable to initiate the cure of the cycloaliphatic epoxy resin(CE) in a second thermal stage. Depending on the proportion of HBP, thermal or photocuring of the epoxy resin took place in different extent, leading to networks with different structures. The photocuring procedure was followed by FTIR and the thermal second stage by DSC. The materials obtained were characterized by DMTA, TGA and SEM. The addition of HBP-Allyl and the trithiol to the formulation allowed increasing the Tg on comparison with the neat epoxy thermoset. The system proposed constitutes a new two-stage dual photo-thermal curing procedure for cycloaliphatic epoxy resins with a thermal latent character.