The purpose of this study is to present the poly(caprolactone) (PCL) functionalization by the covalent grafting of poly(sodium styrene sulfonate) on electrospun scaffolds using the "grafting from" technique and evaluate the effect of the coating and surface wettability on the biological response. The "grafting from" technique required energy (thermal or UV) to induce the decomposition of the PCL (hydro)peroxides and generate radicals able to initiate the polymerization of NaSS. In addition, UV irradiation was used to initiate the radical polymerization of NaSS directly from the surface (UV direct "grafting from"). The interest of these two techniques is their easiness, the reduction of the number of process steps, and its applicability to the industry. The selected parameters allow controlling the grafting rate (i.e., degree of functionalization). The aim of the study was to compare two covalent grafting in terms of surface functionalization and hydrophilicity and their effect on the in vitro biological responses of fibroblasts. The achieved results showed the influence of the sulfonate functional groups on the cell response. In addition, outcomes highlighted that the UV direct "grafting from" method allows to moderate the amount of sulfonate groups and the surface hydrophilicity presents a considerable interest for covalently immobilizing bioactive polymers onto electrospun scaffolds designed for tissue engineering applications using efficient post-electrospinning chemical modification.