To develop high-performance polyacrylicester (ACM) elastomeric components with higher scorch safety and superior thermal and mechanical properties, we replaced aliphatic diamine curatives with aromatic dianiline curatives. The influence of dianiline curatives 4,4′-(4,4′-isopropylidenediphenyl-1,1′-diyldioxy)dianiline, 4,4′-(hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline, and 4,4′-(1,1′-biphenyl-4,4′-diyldioxy)dianiline on the network structures and thermal, dynamic mechanical, and mechanical properties of ACM vulcanizates was investigated. The kinetics of vulcanization was analyzed for different dianiline curatives, with the use of rheometer curves. To understand the electronic properties and study the relation between chemical structure and reactivity, density functional theory was used. The time–temperature superposition principal was used to evaluate the activation energy for degradation of cross-linked samples. Finally, the curing mechanism of ACM in the presence of dianiline curative was studied with X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. These spectroscopic analyses suggested that the reaction mechanism took place via two steps: the first step was formation of the amide linkage and the second step was formation of imide linkages.