In this study, we investigated the protonation of the amine group in epoxy resins prepared using amine-based curing agents by theoretical methods. Density functional theory (DFT)-based free-energy calculations of the corresponding deprotonation subreactions showed that the amine group of the epoxy resin is protonated at equilibrium depending on the location of the amine group when the epoxy resin is embedded in water under standard conditions. Additional DFT calculations demonstrate that the energetic barrier for breaking the ether bond of the epoxy resin is lowered by about 0.6 eV as a result of the cooperative effect of H2O dissociation and that the transition-state energy for breaking the amine group bond is lowered by about 0.4 eV after the protonation of the amine group. Comparing the transition-state energies, we predict that the bond breakage of the protonated amine groups is the principal process causing the weakening of epoxy resins under wet conditions.