A simplified method to modify electrospun PCL fibers for better degradation and cytocompatibility is proposed. The surface modification was achieved by preparing fibers having pores and subsequent alkali treatment. The modifications were studied by comparing hydrolyzed PCL mats, porous PCL mats and hydrolyzed porous PCL mats with unmodified PCL mats. The in vitro degradation analyzed in simulated wound fluid and biological response using L-929 cells confirmed surface-hydrolyzed porous PCL fibers as non-cytotoxic with enhanced cell adhesion, viability and degradability. The proposed modification will be suitable to fabricate implantable electrospun scaffolds.