In this paper a range of acid aqueous solutions are studied towards their suitability for developing chitosan nanofibres by electrospinning. It was found that parameters such as type of solvent, pH, concentration of chitosan, viscosity, charge density, applied voltage, solution flow rate, distance from nozzle tip to collector surface and time play a role in the characteristics of the obtained nanofibrous structures. After a preliminary study to select the most suitable composition of the chitosan containing solution (90% acetic acid), a detailed study was done to find the optimal conditions for chitosan nanofibrous structure development. Finally long-term experiments were performed, which showed that the formation of the nanofibrous structure distorts the electrical field.