This study reveals the influence of silica nanoparticles on the cure reactions of a diglycidyl ether of bisphenol A epoxy resin. As soon as the silica nanoparticles are added to the neat resin (1, 3, and 5 vol.-%), the total degree of conversion increases with an increasing amount of nanoparticles, and the cure reaction shows a more complex autocatalytic behaviour, which can not be described by a traditional kinetic model. Results from subsequent thermomechanical analyses confirm an alteration in the microstructure attributable only to the presence of the nanoparticles in the curing stage. An amino-rich interphase around the reactive treated particles is formed, which shifts the resin/hardener ratio, and benefits the homopolymerization of the epoxy and leads to a more highly crosslinked epoxy network. At the same time, the nanophase consists of a core-shell structure with the rigid particle inside and a rubber-like shell because of the excess hardener in this region.