Fundamental understanding of mechanisms of the epoxy-amine curing reaction is crucial for developing new polymer materials. Nearly all experimental studies, to date for elucidating its mechanisms are based on thermometric measurements and thus cannot provide the molecular level details. This study used density functional theory (DFT) methods to examine the mechanism of epoxy-amine poly addition reactions at the molecular level. Different reaction pathways involving both acyclic and cyclic transition state structures were examined for different reaction conditions, namely isolated, self-promoted by amine, catalyzed by alcohol, and in different solvents. The results indicate that the reactions catalyzed by an alcohol dominate the rate over the self-promoted reaction by other amine species and the isolated one in early stages of the conversion. The concerted pathways involving cyclic transition-state complexes are not significant due to their high activation energies. Calculated activation energies are within the experimental uncertainty. In addition, solvent, not steric and electronic effects as suggested earlier, are shown to be responsible for secondary amines to react slower than primary amines.