Non-woven poly(epsilon-caprolactone) (PCL) nanofibers were prepared by electrospinning and type-I collagen was then immobilized on the nanofibers after surface modification by remote plasma treatment. A collagen-coated surface was observed and characterized using scanning electron microscopy (SEM), contact-angle measurement and X-ray photoelectron spectroscopy (XPS). The results confirmed the successful immobilization of collagen on the nanofibers and the great improvement of surface wettability due to coating. The amounts of immobilized collagen were also measured by colorimetry. The results showed that remote plasma treatment can provide higher immobilization of collagen than conventional plasma. Primary human dermal fibroblasts (HDFs) were cultured to evaluate the biocompatibility of collagen-immobilized electrospun PCL nanofibers. The results of MTT testing and SEM showed that collagen immobilization can obviously enhance the attachment spreading and proliferation of HDFs compared with the pristine material. The collagen-immobilized non-woven PCL nanofibers can be expected to be a potential scaffold material for tissue engineering.