Electrospinning is a fabrication process that can produce highly porous nano-scale fiber-based matrices using an electrostatically driven jet of polymer solution. This method represents an attractive approach for polymeric biomaterial processing which provides the membrane structure that may retain mechanical strengths, flexibility, and high surface area. In this study, we prepared a guided bone regeneration (GBR) membrane with selective permeability, hydrophilicity, good mechanical strength and adhesiveness with bone using polycaprolactone (PCL) and Tween 80 by the electrospinning method. The prepared PCL and PCL/Tween 80 electrospun sheets were characterized via morphology observation, mechanical property, water absorbability, and model nutrient permeability. It was observed that the PCL/Tween 80 (3 wt%) electrospun sheet have an effective permeation of nutrients as well as the good mechanical strength to maintain a secluded space for the bone regeneration. From the results, the hydrophilized PCL/Tween 80 (3 wt%) electrospun sheet seem to be a good candidate as a GBR membrane.