Asymmetric polycaprolactone (PCL) hollow fiber was prepared by wet spinning method for the guidance on the proliferation of Schwann cells. The PCL was dissolved in DMAc as solvent incorporated with tween20 as a pore former to modify the structure and the isopropanol solution was used as a soft coagulant. The dope solution with 18wt.% tween20 and 18wt.% PCL was extruded simultaneously with 15% (v/v) isopropanol solution as bore solution from the annulus-shape nozzle. After passing through 10-cm residence air gap, the fiber was immersed in the 25% (v/v) isopropanol solution bath where coagulation occurred. Scanning electron microscope was used to observe the morphologies of the prepared hollow fibers. The results indicated that the hollow fiber inner surface had pore sizes ranging from 10 to 15 micron. On the other hand, the outer surface was smooth and dense. Furthermore, tensile mechanical properties and thermal properties of the PCL hollow fiber were measured. The culture of Schwann cells inside the hollow fiber was also evaluated.