In this work, a nozzle-free electrospinning device was built to obtain high-throughput production of silk fibroin-based biocompatible composite fibers with tunable wettability. Synthetic biomaterials tend to present suboptimal cell growth and proliferation, with many studies linking this phenomenon to the hydrophobicity of such surfaces. In this study, electrospun mats consisting of Poly(caprolactone) blended with variant forms of Poly(glycerol sebacate) (PGS) and regenerated silk fibroin were fabricated. The main aim of this work was the development of fiber mats with tunable hydrophobicity/hydrophilicity properties depending on the esterification degree and concentration of PGS. A variation of the conventional protocol used for the extraction of silk fibroin from Bombyx mori cocoons was employed, achieving significantly increased yields of the protein, in a third of the time required via the conventional extraction protocol. By altering the surface properties of the electrospun membranes, the trinary composite biomaterial presented good in vitro fibroblast attachment behavior and optimal growth, indicating the potential of such constructs towards the development of an artificial skin-like platform that can aid wound healing and skin regeneration.