Poly(disulfide)s are an emerging class of dynamic covalent polymers with a wide range of applications in medicine, energy, and functional materials such as 3D printing resin, degradable adhesives, and elastic ceramics. However, the constituent dynamic S−S bonds impose a persistent challenge to the precision synthesis of poly(disulfide)s. Leveraging the versatility of supramolecular interactions, we seek to develop new organocatalytic systems to control the synthesis of poly(disulfide)s and design new monomers from bio-renewable resources. From batteries to antibiotics, the well-defined poly(disulfide)s will be exploited for applications in new grounds.