Abstract: | Application of new strategies for supramolecular self‐assembly can significantly impact the properties and/or functions of supramolecular polymers. To realize a facial strategy for the development of solvent‐free supramolecular polymers in bulk, “deep eutectic solvents” were employed. Cyclodextrins and natural acids were used to prepare deep eutectic supramolecular polymers ( DESP s). Deep eutectic solvents have special characteristics that endow DESP s with unique macroscopic properties and excellent processability. DESP s exhibit supramolecular adhesion and temperature‐dependent behavior originating from the combined effects of deep eutectic solvents and supramolecular polymerization. Because DESP s are solvent‐free and display interesting macroscopic properties, they have potential as new adaptive materials. |