PCL fiber web was fabricated through solution/melt electrospinning of PCL resin. PCL nanofibers were obtained by solution electrospinning of 10.5 wt% PCL solution and the resulting average fiber diameters were varied with the range of 150-500 nm. Melt electrospinning method has the advantage of solvent-free process and it is more eco-friendly than solution electrospinning process. The relationship between processing conditions and fiber morphologies of melt electrospun fibers was investigated and it was found that the temperature in the syringe and flow rate were the main factors in determining the average fiber diameter. In addition, thermal properties of PCL fibers obtained by solution/melt electrospinning were compared with PCL chip.