We evaluated the cure behavior of multi-walled carbon nanotubes (MWCNTs) based thermally conductive adhesive by comprehensively thermal analysis, which presented extremely complicated variability of conversion ratio α as a function of temperature with synergistic action of positive effect and negative volumeblocking effect of MWCNTs and cross-linked network of cured polymer molecules. Due to the decomposition of MWCNTs and degradation of polymer, the mass drop is dramatically obvious over the temperature range of 330–370 °C. Binary resins filled with acid -treated MWCNTs present similar reaction interval as neat epoxy and matrix resins, which is distinct from the material filled with raw MWCNTs. The alteration of the crystalline temperature and cure temperature of resins is attributed to heterogeneous nucleation of MWCNTs in matrix resins. The -COOH group of acid-treated MWCNTs reacts with epoxy groups and thus generates cross-linking, accelerates the reaction rate and reduces the cure temperature.