Polyhedral oligomeric silsesquioxane (POSS) can be added to polymers to prepare the organic/inorganic hybrid materials. Octaepoxysilsesquioxane (E-POSS) containing eight reactive epoxy groups in a molecule is one of the important POSSs. E-POSS was cured with methylnadic anhydride (MNA) in this study. The curing kinetics of the E-POSS/MNA system was studied by using differential scanning calorimetry (DSC). Two different kinds of methods, Kinssinger and Flynn-Wall-Ozawa, were used to calculate the activation energy and pre-exponential factor of the curing reaction.