To overcome the problems related to the low surface enrichment of blended fibers from hydrophilic polymer, routine blend electrospinning setup was modified by exposing the polycaprolactone (PCL)-Pluronic P123 solution to water in order to attract the hydrophilic chains toward the fiber surface. Analysis of the modified fibers revealed a drastic surge of hydrophilic polymer surface enrichment value in comparison with that of the routine method which suggested homogenously positioned Pluronic on the surface and the subsequent reduction of its accumulations within fibers. The thermogram of the proposed method showed induced crystallization in the Pluronic section. Furthermore, the intensity of PCL characteristic peaks decreased for this method.