In this study, the surface morphology of electrospun polycaprolactone (PCL) fibers was investigated. PCL was dissolved in various solvent/nonsolvent systems (acetone/dimethylformamide (DMF), tetrahydrofuran (THF)/DMF, dichloromethane (DCM)/DMF, chloroform (CF)/DMF, acetone/dimethyl sulfoxide (DMSO), THF/DMSO, DCM/DMSO, CF/DMSO) at a fixed ratio of 80/20 v/v. PCL solutions from these solvent systems were electrospun under varying high relative humidity (60-90%), and also room humidity. Characterization of fibers was evaluated by a scanning electron microscope, an atomic force microscope, water contact angle measurements, the Brunauer-Emmett-Teller method, and a strain-stress test. Results revealed that the surface texture of individual fibers changed with the presence of different types of pores and surface roughness depending on both humidity and solvent/nonsolvent properties. Miscibility with water was another factor to be taken into account for understanding mechanisms that contributed to the formation of surface defects. Fibrous materials having such a surface architecture, especially the porous ones, are potential candidates for various applications such as tissue engineering, drug delivery, catalysis, and filtration.