The curing behavior of the glycerol diglycidyl ether/3,3-dimethylglutaric anhydride/nano-alumina system was examined using a dynamic differential scanning calorimetry technique. The activation energy of the system was calculated using the Kissinger, Ozawa, Barrett, and two-parameter Sestak–Berggren models. Under the assumption of a constant activation energy and an autocatalytic mechanism, the activation energy, frequency factor, and total order of reaction were computed. The theoretical reaction rate was also calculated and compared to the experimental results. Good agreement was seen between the experimental and calculated data confirming the autocatalytic mechanism. The effect of triethylamine concentration on the reaction rate was clarified using the Barrett method. Fourier transform infrared spectroscopy (FT-IR) spectroscopy was used to verify the formation of internal ester groups. Scanning electron microscopy (SEM) and X-ray mapping analyses revealed that the nanofiller was homogeneously distributed in the continuous phase.