Mechanical properties measurements, like Charpy impact tests, provided evidence that the macromolecular network of the epoxy system formed by the hexafunctional triethylene tetramine hardener, TETA, with the diglycidyl ether of bisphenol A monomer, DGEBA, can be modified by changing the hardener content. The previously analyzed monomer-to-hardener ratios were here studied by C-13-NMR solid state techniques. The results from crosspolarization/magic angle spinning (CPMAS) C-13-NMR spectra, together with the evaluation of proton spin-lattice relaxation time in the rotating frame (T(1)(H)rho), display the behavior of these epoxy/hardener mixtures considering the mobility and interaction of molecular segments present at the macromolecular structure. The results also show that the epoxy-rich mixtures form tight, and therefore brittle, structures as previously observed by mechanical tests. The stoichiometric monomer-to-hardener ratio is a transition point where an increase in the mobility was found. For the amine-rich mixtures the obtained results suggest the presence of domains with different segmental mobilities.