Reproducible buckled and porous sub-micron diameter polycaprolactone (PCL) fibers were produced by simple electrospinning process for biomedical applications. In this study, six types of solvent combinations with different vapor pressures were used to study the effect of phase separation on the morphology of electrospun fibers. The fiber morphology, Infrared spectroscopy, water contact angle and tensile test were performed to study the material properties. It is evident that the fiber morphology was affected by solvent combinations used for the fabrication of sub-micron fibers. The solution viscosity, the collecting distance and the type of solvent combination used could be an optimum parameter for the generation of porous-buckled fibers with narrow pore size distribution. The simplicity of the set-up is the immense advantage for producing buckled and porous elastomeric fibers for tissue engineering applications. All the fibers were spun on a motionless collector plate to study the properties of fibers. The combination of surface pores with the buckled pattern could be of great importance in the field of biomedical engineering. (C) 2014 Elsevier Ltd. All rights reserved.