In this study, medical-grade polyvinyl alcohol (PVA) is used as the base material and made into PVA nanofiber membranes via electrospinning. Meanwhile, urushiol is extracted from raw lacquer collected from sumac using the rotary steaming method. Combined with urushiol as a sustained-release agent and coordination agent, the PVA nanofiber membranes are examined for their sustained-release performance. Moreover, visual observation in an animal study serves as the qualitative test, while ELISA inflammatory factors serve as the quantitative test. It is confirmed that PVA mitigates the allergies caused by urushiol. Furthermore, nano-zinc oxide is incorporated as an antibacterial agent, and the coordination effect between urushiol and 1 wt% of nano-zinc oxide achieves antibacterial effectiveness greater than 95%. In addition, the nanofiber membranes are loaded with l-ascorbic acid and etamsylate to accelerate wound repair and hemostasis, respectively. UV/Vis analysis confirms the function of urushiol as a sustained-release agent. The one-step method provides PVA with insolubility while retaining the sustained-release function. Therefore, urushiol can act as an antibacterial agent, coordination agent, and sustained-release agent, which expands its application range while broadening the compatible effective ingredients for nanofiber membranes as wound dressings.