Deep eutectic solvents (DESs) are considered "green" and "sustainable" alternatives to conventional organic solvents and ionic liquids (ILs) due to their characteristic properties and relatively low costs. DESs are considered IL analogs and have attracted consideration as benign media formulations for the synthesis of novel polymers because they satisfy the principle of sustainability. Over the past few years, the use of DESs has resulted in novel pathways for the synthesis of novel materials, biomaterials, functional materials, and ionic soft materials. Furthermore, DESs have been widely applied in the science, industrial, engineering, and technological fields. On the other hand, stimulus-responsive (smart) polymers have been widely utilized in intelligent devices owing to their virtues of good processibility, stimuli and environmental sensitivity, responsivity, and so on. With the introduction of a DES into the smart polymeric matrices, their potential characteristics, biocompatibility, and flexibility endow the corresponding DES-based polymeric materials with intriguing properties, which in turn will broaden their applications in various domains of polymer science and material chemistry. Substantial research has been done in the fabrication of DES-based polymeric materials. Numerous studies have extensively investigated the effects of DESs on biomolecules such as proteins/enzymes and nucleic acids, whereas few have addressed the impact of DESs on the aggregation and phase transition behaviors of smart polymers. This review focuses on mechanistic insights, aggregation behavior, and interactions between smart polymers and DESs. Opportunities and future research perspectives in this blossoming arena are also discussed. It is hoped that this review will pave futuristic pathways for the design and development of advanced DES-based polymeric materials and biomaterials for various applications.