Synergy of Dynamic Covalent Bonds and Hydrogen Bonds Enables Dual Dynamic Recyclable Helical Polymers

• • The helical poly(disulfide) system achieves complete chemical recyclability to monomers, with depolymerization monitored in real-time at 363 K in C2H2Cl4, demonstrating closed-loop recycling under mild thermal conditions. • • Incorporation of the dipeptide motif AA-L-Ala-L-Ala establishes stable β-sheet-like hydrogen bonds, increasing helical content and stability, as evidenced by temperature-varied CD and UV-vis spectra at 3 g L−1 in C2H2Cl4. • • Thermal treatment reorganizes nanocrystalline polymers into semicrystalline rod-like flexible cylinders with diameter ~2.1 nm and length ~25 nm, enabling hierarchical assembly into columnar liquid crystal phases. • • The dual dynamic system (dynamic disulfide bonds and hydrogen bonds) provides conformational resilience up to high temperatures, maintaining rod-like shape and helical conformation, which is critical for applications requiring thermal stability and recyclability.