Layer-by-layered micro/nanofibrous mats consisted of poly(E >-caprolactone) (PCL) and poly(ethylene oxide) (PEO)/Rhodamine-B (RM), which is used as an indicator of drug release, were fabricated by using a modified electrospinning process to observe the release of RM from the layered mats. In this study, we focused on the edge-effect of the layer-by-layered electrospun mats, because the initial burst release from the layered mats occurred in the edge area of the mats. To overcome this deficiency, we proposed a new electrospun layer-by-layered mat, where the edge of the PEO/RM layer was completely covered with the PCL layer controlling the releasing drug. From the cumulative releasing behavior of the drug, we could observe that the drug release was well controlled regardless of the length of edge, and the initial burst was readily adjustable.