Cure kinetics of epoxy nanocomposites containing multi-walled carbon nanotubes (MWCNTs) was studied by differential scanning calorimetry and rheological analyses. A very low content of pristine and amine-modified MWCNTs were introduced into epoxy resin to study the agreement of calorimetric and rheological methods on cure kinetics assessment of epoxy/MWCNTs nanocomposites. In this way, Model-free and model-fitting methods were used to gives rise the more useful information about cure kinetics of studied samples. As expected, incorporation of unmodified MWCNTs into epoxy resin increase activation energy caused by physical hindrance, while for modified MWCNTs, it decline. This is mainly because of existing amine groups on the filler surface that accelerate the curing reaction. Isothermal rheokinetic studies reveal the crosslinking structure of epoxy resin in the presence of various amount of MWCNTs content. Accordingly, 0.3 wt.% MWCNTs impede the curing reaction as well as destruct the 3D crosslinking network.