Hydrogels have been widespreadly used in various fields. But weak toughness has limited their further applications. In this study, Dendrobium officinale enzyme (DOE) was explored to improve chitosan/γ-poly(glutamic acid) (CS/γ-PGA) hydrogel in the structure and properties. The results indicated that DOE with various sizes of ingredients can make multiple noncovalent crosslinks with the skeleton network of CS/γ-PGA, significantly changing the self-assembly of CS/γ-PGA/DOE hydrogel to form regular protuberance nanostructures, which exhibits stronger toughness and better behaviors for skin care. Particularly, 4% DOE enhanced the toughness of CS/γ-PGA/DOE hydrogel, increasing it by 116%. Meanwhile, water absorption, antioxygenation, antibacterial behavior and air permeability were increased by 39%, 97%, 27% and 52%.