To achieve excellent biofunctionality of Bombyx mori silk fibroin (SF), we explored a novel hybridization method to combine the unique properties of SF with poly(epsilon-caprolactone) (PCL) electrospun fibers. The hybrid electrospun fibers demonstrate excellent hydrophilicity and biocompatibility that are important to tissue engineering applications. The biomimetic fibrous structure was fabricated by conventional electrospinning of PCL. The individual surfaces of PCL electrospun fibers were coated with silk fibroin protein using a lyophilization technique. The SF coating layers were durable which were further developed by surface modification with fibronectin to improve their biological function. The hybrid electrospun fibers show excellent support for normal human dermal fibroblast (NHDF) cells adhesion and proliferation than neat PCL fibers, while the surface-modified hybrid electrospun fibers show significantly enhanced proliferation of NHDF cells on their surface. This study indicates the new opportunity of fabrication technique that can construct a biomimetic fibrous structure while the original function as a biomaterial remained existing. (c) 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41653.