Nanofibrous mats of poly ε-caprolactone (PCL) were fabricated by electrospinning. The nanofiber structures were investigated and characterized by scanning electron microscope, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, static water-contact-angle analysis and mechanical properties. The results showed that the nanofibrous PCL is an ideal biopolymer for cell adhesion, owing to its biocompatibility, biodegradability, structural stability and mechanical properties. Differential scanning calorimetry results showed that the fibrous structure of PCL does not alter its crystallinity. Studies of the mechanical properties, wettability and degradability showed that the structure of the electrospun PCL improved the tensile modulus, tensile strength, wettability and biodegradability of the nanotemplates. To evaluate the nanofibrous structure of PCL on cell adhesion, osteoblasts cells were seeded on these templates. The results showed that both adhesion and proliferation of the cells is viable on these electrospun PCL membranes. Thus electrospinning is a relatively inexpensive and scalable manufacturing technique for submicron to nanometer diameter fibers, which can be of interest in the commodity industry.