Due to the ability to fabricate fibrous scaffolds with micro and nano-scale properties, electrospinning technique has received much interest. Poly(caprolactone) (PCL) fibrous scaffolds with micro and nano-scale fibers and surface-porous fibers have not been explicitly investigated. In this study, the results of modulating the factors on processing route on fibrous scaffold morphology were investigated. 10% w/v and 13% w/v PCL in dichloromethane (DCM) or chloroform was used at different flow rate and applied voltage. The result showed 13% w/v PCL/chloroform produced better fibers with porous bimodal distribution fiber sizes. The porous fibrous scaffolds had two different ranges of fiber diameters. Average fiber diameter in the higher range was 4 μm to 9 μm while average fiber diameter in the lower range was 400 nm.