The development of multifunctional epoxy thermosets that meet the requirements of sustainable development by creating new macromolecular architectures, i.e., novel epoxy monomers, is a real challenge. Herein, a bis-imidazolium cycloaliphatic epoxidized room temperature ionic liquid (CEIL) was successfully synthesized at multigrams scale (1−200 g) and used as molecular brick platforms to design various networks combined to a computational approach. Thus, three epoxy networks were developed by cationic polymerization using CEIL and 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate (ECC) in the presence of a thermoacid initiator. The CEILbased networks presented higher thermal stabilities (>450 °C) and good mechanical performances combined for promising shape memory behavior. Most importantly, the incorporation of this ionic molecular brick, i.e., CEIL monomer in the architecture of the networks (50% or 100%), addresses the concept "design to degrade" inducing full degradability for the first time under mild working conditions (up to 99.4% of p-CEIL dissolution in 4.5 h).