Hydrogels have considerably emerged in a variety of fields, but their weak mechanical properties severely restrict the wide range of implementation. Herein, we propose a multiscale hydrogen bonding toughening strategy using saccharide-based materials to optimize the hydrogel network. The monosaccharide (glucose) at the molecular scale and polysaccharide (cellulose nanofibrils) at the nano/micro scale can effectively form hydrogen bonds across varied scales within the hydrogel network, leading to significantly enhanced mechanical properties. Besides, the toughened hydrogels present excellent environmental resilience and bad solvent resistance, allowing them to retain their performance in various severe environments. Notably, after being exchanged with a bad solvent such as ethanol, the alcogel exhibits strain-depended vivid interference color, allowing it to function as a mechano-optical sensor. Finally, this strategy has been shown to be adaptable across multiple material systems, and the resulting hydrogels have potential as a bioelectronic interface for long-term stable recording of physiological signals, highlighting the potential of sustainable biomaterials in designing high-quality hydrogels for advanced applications.