In this study we engineered bilayered electrospun scaffolds consisting of hydrophobic PDLLA and hydrophilic PVP layer which incorporate either native HA or semi-synthetic HA-Gly-OH at concentrations of 1% and 3% w/w. Generally, bilayer scaffolds electrospun on different days delaminated, while herein they maintained their integrity because electrospun on the same day. Sequential electrospinning enabled the bilayer structure, characterized via Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), and Young’s modulus measurements to assess morphology and mechanics. In vitro cytotoxicity and cell viability assays with fibroblast cells confirmed good biocompatibility for both the individual layers and bilayer system. Among the tested formulations, the bilayer PDLLA/PVP–HA-Gly-OH 1% showed the most promising performance, attributed to the synergistic effects of HA and Gly-OH in promoting adhesion and proliferation.