Infected wounds pose a significant global health challenge due to the persistence of bacterial biofilms and limited tissue self-repair. Nitric oxide (NO) functions as a potent antimicrobial agent, demonstrating a dual capacity for both antimicrobial action and tissue rejuvenation across varying concentrations. However, achieving controlled NO release at distinct stages of infected wound progression, simultaneously targeting biofilm removal and wound recovery, remains a formidable challenge. In this work, we introduce a smart electrospun fibrous membrane, featuring an interior laden with NO-loaded HKUST-1 particles and a porous external surface. Notably, the results reveal the photothermal property of HKUST-1 when exposed to near-infrared (NIR) light, enabling precise management of NO release contingent upon light conditions. During the initial phase of infection treatment, a significant NO release is triggered by near-infrared photothermal stimulation, synergistically complementing photothermal therapy to effectively eliminate bacterial biofilms. Subsequently, in the wound-healing phase, NO is released from the degrading fibrous membrane in a controlled and gradual manner, synergizing with trace amounts of copper ions released during MOF degradation. This collaborative mechanism accelerates the formation of blood vessels within the wound, thereby facilitating the healing process. This study suggests a promising and innovative approach for the effective treatment of infected wounds. A smart electrospinning fibrous membrane that can intelligently release NO at different stages of infected wound treatment was designed, which could eliminate biofilm and promote the healing of infected wounds.