Abstract The excessive consumption of petroleum‐derived polymers has resulted in resource depletion and severe environmental pollution, underscoring the need for sustainable alternatives based on natural bio‐derived molecules. Owing to its abundance, tunable molecular structure, and inherent dynamic responsiveness, thioctic acid (TA) has recently emerged as a promising building block for functional supramolecular materials. Through diverse ring‐opening polymerization (ROP) pathways, TA can form polymeric networks containing dynamic disulfide bonds, thereby imparting reconfigurability, programmability, and adaptive functionality. These features enable a broad range of applications in flexible sensors, energy devices, biomedical systems, and intelligent adhesives. Although numerous novel perspectives have recently emerged regarding TA, such as self‐assembly, specific applications, and biomaterials, ROP methods for TA and the interdisciplinary advancements in its functional applications remain incomplete. Therefore, this review innovatively proposes a classification framework to systematically elaborate upon the design principles and synthetic strategies for TA‐based supramolecular materials. Moreover, this review highlights the interdisciplinary functional applications of TA‐based supramolecular materials and discusses current challenges and future opportunities to provide practical guidance for the development of next‐generation sustainable materials.