Surgical adhesives are crucial for achieving rapid hemostasis and immediate wound management during clinical interventions. However, developing a tissue adhesive that combines instant adhesive strength with biodegradability in dynamic, wet, or hemorrhagic biological environments remains a persistent challenge. Here, a biodegradable supramolecular tissue adhesive with robust instant adhesion to wet tissue surfaces within 5 s is presented. The distinctive synergy of surface‐rich adhesive groups and the hydrophobic main chain enables the adhesive to surmount the hydration layer on the tissue surface, ensuring rapid adhesion. Importantly, the internal structure of this supramolecular adhesive significantly contributes to its exceptional holding adhesion strength. Additionally, in vivo experiments using a rat liver incision model and a skin injury model are conducted. These experiments demonstrate its effectiveness in emergency hemostasis and wound management. Consequently, this supramolecular tissue adhesive exhibits significant potential in surgical applications, addressing critical needs in urgent clinical scenarios and potentially making valuable contributions to the medical field.