Pectin is a natural polymer present in plants and, as all natural polymers has biodegradation properties. Chemically, pectin is a polysaccharide composed of a linear chain of 1→4 linked galacturonic acids, which is esterified with methanol at 80%. The pectin-based gel electrolytes in a transparent film form were obtained by a plasticization process with glycerol and addition of LiClO4. The films showed good ionic conductivity results, which increased from 10−5 S/cm for the samples with 37wt.% of glycerol to 4.7×10−4 S/cm at room temperature for the sample with 68wt.% of glycerol. The electrochemical behaviors of the samples were studied by electrochemical impedance spectroscopy (EIS), and Nyquist graphs are showed and discussed. The obtained pectin-based samples also presented good adherence to the glass, flexibility, homogeneity (SEM) and transparency (about 70% in the vis) properties. They are good candidates to be applied as gel electrolytes in electrochromic devices.