Ultra-fine fibers of zein/poly(e-caprolactone) (PCL) composites were prepared by oriented electrospun technology to enhance the toughness and ductility of zein. The mechanical, morphological and thermal properties of fibrous films of zein/PCL were studied by texture analysis and nanoindentation tests, scanning electron microscopy and dynamic mechanical analysis. Wettability of fibrous films was also measured and discussed. The mechanical properties of these fibrous films were significantly improved with the addition of PCL. Research on the antibacterial activities of poly(e-lysine) (EPL) loaded films of zein/PCL/poly(e-lysine) shows that the films could inhibit the growth of Listeria monocytogenes. Films of zein/PCL blend systems with a hydrophilic surface do not dissolve in water and have excellent toughness and ductility. This is very favorable for applications in biodegradable materials, food packing materials, facial masks and as antimicrobial films for wound dressing.