Dielectric Thermal Analysis (DETA) of a series of new thermoset obtained by click chemistry was performed. The new thermosets were obtained by a dual-curing process consisting in a first photochemical thiol-ene, followed by a thermal thiol-epoxy starting from an allyl-terminated hyperbranched poly(ethyleneimine) (HBPEI) and different proportions of diglycidylether of bisphenol A (DGEBA) and the corresponding stoichiometric proportions of pentaerythritol tetrakis (3-mercaptopropionate, PETMP). The dielectric behaviour was obtained experimentally supressing the conductive effects. Two sub-Tg intramolecular non-cooperative γ and β relaxations and an intermolecular cooperative α-relaxation were detected. The γ-relaxation was ascribed to the dipole orientation of the terminal thiol groups. Two γ relaxations γepo and γene were observed, according to the influence of the surroundings. Only thermosets with a content of flexible HBPEI/PETMP domains higher than a 50% w/w showed the γene relaxation at lower temperatures and higher frequencies. The β-relaxation was a non-Johari-Goldstein relaxation, ascribed to the dipole transfer of the linear CH2O(CO)CH2CH2 groups of the thiol constrained in the glassy state. The α-relaxation was ascribed to the long-term segmental movements of the thermosets, occurring during the transition from the glassy to the rubbery stage. A synergic effect of reducing the rigidity and compactness of the thermosets by the reduction of aromatic moieties of the DGEBA/PETMP units, and the increase of the flexibility induced by the addition of HBPEI/PETMP units affected the macromolecular movement of the thermosets.