New epoxy thermosets have been prepared via cationic UV-photopolymerization introducing two different multiarm star-like polymers. Both stars have a poly(glycidol) core but one has poly(methylmetacrylate) arms and the other poly(ε−caprolactone) ones. The characterization of the curing process has been performed by Real-Time FTIR and photo-DSC, observing a slight reduction in the curing rate on increasing the proportion of star. The thermosets prepared were characterized by gel content determination, DMTA and TGA, and finally the morphology observed by FE-SEM, demonstrating the formation of nanophases in the case of the star with poly(ε−caprolactone) arms. POLYM. ENG. SCI., 54:17–23, 2014. © 2013 Society of Plastics Engineers