Hydrogel dressings have attracted extensive attention owing to the similarity in their softness to that of the extracellular matrix, adjustability of physicochemical properties, and ability to remain moist even at the wound site. However, developing composite hydrogel with excellent mechanical behavior, adhesiveness to tissues, good biocompatibility, long‐term antibacterial properties, and enhanced vascularization capacity continues to be a great challenge. Herein, a novel nanocomposite hydrogel based on the photo‐cross‐linking of poly(ethylene glycol)diacrylate (PEGDA), thiolated chitosan (TCS), and modified polyhedral oligomeric silsesquioxane (POSS) nanoparticles is designed. Moreover, silver ions (Ag+) are loaded into the system via dynamic coordination of Ag–S. The resultant PEGDA/TCS/POSSP@Ag hydrogel presents high toughness, strength, and good tissue adhesiveness and facilitates the attachment and proliferation of human umbilical vein endothelial cells (HUVCEs) in vitro. As a controlled release carrier of the bacteria‐killing activity of Ag+, the composite system achieves controlled release of Ag+ and good antibacterial activity. Further in vivo experiments demonstrated that the PEGDA/TCS/POSSP@Ag scaffolds significantly promote skin regeneration by reducing inflammation and inhibiting infection, a rat model with full‐thickness skin defects verified its ability to stimulate microvascular formation due to activation of POSS. Thus, the multi‐functional nanocomposite hydrogel is a highly promising dressing material for wound healing.