The thermodynamics of newly designed tri- and tetraepoxyimidazolium NTf2 monomers reacting with several diamines used as curing agents to form epoxy/amine thermosets was studied. The ability of each epoxy/amine combination to induce cross-linking both through the substitution of multiple epoxy groups and through multiple additions to a single amine was investigated. Through an increased understanding of the thermodynamics of epoxy-amine polymerization in complex polyepoxy-ILs, it is possible to more thoroughly understand the factors affecting the reactivity in these complex systems. These calculations showed that while each possible epoxy-amine combination was exergonic to both forms of cross-linking, the degree to which both amines-induced cross-linking and epoxy-induced cross-linking was favored varied between epoxy-amine combinations. Thermodynamic results obtained using density functional theory were experimentally validated through differential scanning calorimetry results, wherein similar trends were noted between theory and experiment. Among the trends noted in amines-epoxy combinations tested, tetraepoxyimidazolium NTf2/PACM (i.e., a cycloaliphatic diamine) was found to be a prime candidate for amine cross-linking, with the addition of a second epoxy to a single amine group being notably the most negative of all epoxy-amine combinations at -77.6 kJ mol-1. While in the case of epoxy cross-linking, the aliphatic polyetheramine denoted Jeffamine-D230-containing systems were found to be the most exergonic, with additions of primary amines to triepoxyimidazolium and tetraepoxyimidazolium NTf2 averaging -86.9 kJ mol-1. Interaction energy analysis indicated that the aromatic amine named sulfanilamide is the most favorable to engage in reactions due to having the most negative interaction energies with already highly substituted epoxy monomers. These results can be used to adjust the cross-linking possibilities of tri- and tetraepoxyimidazolium NTf2/amine polymerization and give insight into the predominant cross-linking reactions in these unique systems.