Postoperative adhesion may form as the result of a complicated fibrosis and inflammatory response, thus leads to a series of complications or increases the risk of surgery failure. Herein, we prepared poly (lactic-co-glycolic acid)-graft-polyvinylpyrrolidone/polyiodide (PLGA-g-PVP/I) electrospun fibrous membranes to prevent postoperative adhesion and infection formation. Firstly, hydrophilic PVP molecules were grafted on the surface of PLGA powders by gamma ray, and then iodine ions were coordinated with the grafted PVP. Subsequently, PLGA-g-PVP/I fibrous membranes were prepared by electrospinning. The PLGA-g-PVP/I membranes were analyzed via UV vis, FTIR, Raman, and XPS. The formed polyiodide endowed the membranes with sustained antibacterial activity. The antimicrobial property of PLGA-g-PVP/I membranes was ascribed to the synergistic effect of intracellular ROS production and glutathione oxidation. Furthermore, the prevention efficacy of postoperative abdominal adhesion from the PLGA-g-PVP/I composite membranes was characterized in a rat model of sidewall defect-cecum abrasion. The results demonstrated that the PLGA-g-PVP/I fibrous membranes could prevent the postoperative abdominal adhesion effectively. Therefore, to endow the PLGA-g-PVP/I electrospun fibrous membranes with durable antibacterial property may be a promising strategy towards an anti-bacterial and anti adhesion system for commercial and clinical uses.