In this study, we prepared electrospun polycaprolactone/polyethylene oxide (PCL/PEO) membranes fabricated by electrospinning. We designed the membranes for the application of medical patch. In order to understand the drug-released behavior when the membranes were used in medical patch, ketoprofen was used as a model drug. The results show that ketoprofen-loaded electrospun membranes that comprised PCL/PEO released all ketoprofen in 30 min. The mebranes had potential application in medical patch. In additions, the viscosity of the PCL/PEO solution increased with the proportion of PEO. The low conductivities of the all PCL/PEO solutions were caused by the lack of electric charge on both PCL and PEO molecules. A higher PEO percentage was associated with high enthalpy of fusion of the electrospun PCL/PEO membrane. The crystallinity of PEO in the PCL/PEO composite decreased as the PEO content declined.