Serious skin damage caused by trauma, surgery, burn or chronic disease has become one of the most serious clinical problems. Therefore, there is an increasing demand for ideal wound dressing that can improve wound healing. Due to the vital role of nitric oxide (NO), we developed a novel functional wound dressing by combining electrospun polycaprolactone (PCL) mat with NO-releasing biomaterial (CS-NO). The sustained release of NO from PCL/CS-NO demonstrated positive effects on wound healing, including pro-angiogenesis, immunomodulation, and enhanced collagen synthesis. Hence, wound healing process was remarkably accelerated and the organization of regenerated tissues was effectively improved as well. Taken together, PCL/CS-NO dressing may be a promising candidate for wound treatment, especially for the chronic wound caused by the ischemia.