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Bacterial infection and dehydration are two dominant issues that limited the effectiveness of the available treatments in re-establishing the structure and functions of damaged skin. Currently, electrospinning, that using electrostatic forces to fabricate polymeric nanofibre, has received blooming attention in the invention of ideal skin scaffold because of its ability to produce multifunctional nanofibres that is not only prevented the problems but also mimicked the extracellular matrix to accelerate the wound healing process. In this project, two synthetic polymers, i.e. Poly(vinyl alcohol) (PVA) and Polycaprolactone (PCL), and different amount of a natural polymer, i.e. Chitosan, were blended and electrospun into nanofibre. The presence of synthetic polymers was crucial as they increased the electrospinnability of chitosan. For comparison purposes, the electrospun PVA-PCL nanofibres were also fabricated. Disc diffusion testing was conducted initially and exhibited that the blended nanofibres inhibited the growth of Staphylococcus aureus and Escherichia coli when the content of chitosan reached 1.5 wt%. The infrared spectroscopy result of both PVA-PCL-Chitosan and PVA-PCL showed typical peaks of PVA and PCL at 3327 and 1719 cm-1 represented O-H and C=O bonds, respectively. FESEM images showed that the smaller fibre and bimodal structure nanofibrous mat were obtained when the chitosan was added. Finally, the hydrophilicity of the PVA-PCL-Cs nanofibrous mat was confirmed by water contact angle which is 0° and hypothetically, it could prevent dehydration and improve cell adhesion to accelerate the wound healing process.