A ubiquitous example of DNA and proteins inspires the scientific community to design synthetic systems that can construct various self-assembled complex nano-objects for high-end physiological functions. To gain insight into judiciously designed artificial amphiphilic structures that through self-assembling form various morphological architectures within a single system, herein, we have studied self-aggregation of amide-functionalized surface-active ionic liquids (AFSAILs) with different head groups in the DMSO/water mixed system. The AFSAIL forms stimuli-responsive reversible micelle and vesicle configurations that coexist with three-dimensional (3D) network structures, the organogel in the DMSO/water mixed system. The self-assembly driving forces, self-organization patterns, network morphologies, and mechanical properties of these network structures have been investigated. With the proven biodegradability and biocompatibility, one can envisage these AFSAILs as the molecules with a new dimension of versatility.