Currently, green based materials are receiving attention in a quest to achieving a sustainable environment for human life. Herein, we report an investigation of developing a simple novel green nanofiber by using H2O2-assisted water soluble chitosan/polyvinyl alcohol (WSCHT/PVA) in the presence of water as an eco-friendly solvent.The effect of various process parameters on the mean fibre diameter was investigated based on the Taguchi L9 (3^4) orthogonal array experimental design. Optimal process parameters were determined using the signal-to-noise (S/N) ratio of diameter according to “smaller-the-better” concept. Accordingly, the smallest fiber diameter observed was 122 nm and it was yielded at solution concentration of 10%; a voltage of 16kV; a flow rate of 0.7 mL h-1; and a collection distance of 8 cm. The implications of a green environmentally sustainable material impact on a number of diverse end uses.