The treatment of infected wounds remains a challenging biomedical problem because of the complex microenvironment at the wound bed. Some natural bioactive small‐molecule hydrogelators with unique rigid structures can self‐assemble into supramolecular hydrogels, serving as supporting dressings and therapeutic agents for wound healing. However, they are still suffered from low structural stability and bio‐functionality. Herein, we proposed a supramolecular hydrogel antibacterial dressing with a dual nanofibrillar network structure. A nanofibrillar network created by small‐molecule hydrogelator, puerarin extracted from the traditional Chinese medicine Pueraria, was interconnected with a secondary macromolecular silk fibroin nanofibrillar network induced by Ga ions via charge‐induced supramolecular self‐assembly. The resulting hydrogel features adequate mechanical strength for sustainable retention at wounds. The good biocompatibility and efficient bacterial inhibition were also obtained when the Ga ion concentration was 0.05%. Otherwise, the substantial release of Ga ions and puerarin endows the hydrogel with excellent hemostatic and antioxidative properties. In vivo evaluation on a mouse infected wound model demonstrates that its healing effect outperformed that of a commercially available silver‐containing wound dressing. The experimental group successfully achieved a 100% wound closure rate on day 10 of treatment. This study sheds a new light on the design of nanofibrillar hydrogels based on supramolecular self‐assembly of naturally derived bioactive and/or biofunctional molecules as well as their clinical use for the treatment of chronic infected wounds.This article is protected by copyright. All rights reserved