In this study, mechanically strong hydrogels are synthesized by photopolymerization of 2‐vinyl‐4,6‐diamino‐1,3,5‐triazine, poly(ethylene glycol) methacrylate, and disulfide‐containing cross‐linker, N′N‐bis(acryloyl)cystamine. The bilayer hydrogel with distinct cross‐linking density is shown to self‐roll into a 3D tube, which could still be well reinforced by hydrogen bondings, upon exposing reductants such as 1,4‐dithio‐DL‐threitol (DTT) or L‐glutathione (GSH), because the redox‐induced cleavage of disulfide bonds results in the imbalanced internal shrinking stress between two layers. At an intracellular level of GSH, model L929 cells‐seeded bilayer gel sheet could curl up into a 3D tubular scaffold where the cells maintained good viability.
