New solid polymeric electrolytes were obtained from amylopectin rich starch plasticized with glycerol and containing lithium perchlorate salt. The transparent film samples were characterized by X-ray diffraction and thermal analysis (DSC). The ionic conductivity measurements were obtained by impedance complex spectroscopy as a function of temperature three different salt contents. The conductivity of 5.05.10(-5) S/cm at room temperature were obtained for the samples of starch plasticized with 30% of glycerol and containing [O]/[Li] = 8. These results show that starch is very good material to be used for preparation of new solid polymeric electrolytes.