The aim of this study was to analyze the influence of different acetic acid concentration used in the chitosan/PVA solutions, had on the electroactive response of fibers. Chitosan/PVA fibers were obtained by electrospinning process. The diameters of the electrospun fibers increased as the concentration of acetic acid was higher in solutions. The electroactive properties of the fibers were tested on an electrochemical cell at different pH. The proportion of free amino present of the obtained fibers was determined by deconvoluting the FTIR spectra. Fibers obtained from chitosan/PVA solutions with 10 % of acetic acid had an average diameter of 465 nm, while fiber obtained from solution with 80% acetic acid had an average diameter of 987 nm. The proportion of free amino observed from the deconvolution results was proportionally to the electroactive properties of the material. Fibers obtained from solution containing 30% acetic acid exhibited the fastest speed displacement (2.05 mm s-1), from the deconvolution of its spectra was observed that the proportion of free amino (8.71%) was the highest from all samples