Multiple stimuli‐responsiveness is an attractive property that is studied in physical chemistry and materials chemistry. While, multiple stimuli‐responsive phase change in an isothermal way is rarely addressed for functional materials at room temperature. In this study, one azobenzene‐containing surfactant AZO is designed for the fabrication of triple stimuli‐responsive phase change biomaterial (Alg‐AZO) through the electrostatic complexation with natural alginate. Thanks to the photoisomerization ability, molecular flexibility and hydrophilicity of AZO, together with the tailoring effect of alginate on AZO, Alg‐AZO could perform reversible isothermal phase transition between liquid crystalline and isotropic liquid states under the stimuli of either light or humidity at room temperature. Furthermore, the humidity‐induced isotropic state can also fast transit to ordered state under shear force, owing to the π‐π interactions between planar trans‐AZO in Alg‐AZO material. With good biocompatibility, self‐healing property and in vivo wound healing promoting capacity that is promoted by light, humidity and force, Alg‐AZO would be suitable for working as a new smart biomaterial in biological and biomedical areas. This work provides a designing strategy for gaining multiple stimuli‐responsive smart materials based on biomacromolecules, and also opening a new opportunity for gaining self‐healing biomaterials capable of working in various conditions.