Recent literature on SPEs contains a significant number of reports on application of Starch for solid polymer electrolyte applications [8–12]. Structural studies made on starch have affirmed that starch from almost all species contain water in its structure[13] which favors ion conduction and promotes dissociation of salts to the maximum extent [9]. However these advantages of Starch are often veiled by some flaws that limit its use. Some of the drawbacks are brittles of films, large water absorption, low mechanical strength etc. One way to overcome these shortcomings that has been devised is the blending of Starch with other biodegradable polymers like PVA [7]. It is a versatile synthetic biodegradable polymer that has been reported numerous times for SPE applications Starch and PVA are reported to be miscible with each other via the formation of hydrogen bond [14,15]. In the fabrication of Starch/PVA blends a vital role is played by crosslinkers and plasticizers. Plasticizers reduce the brittleness and glass transition temperature of Starch based films which are fundamental requirements for obtaining higher conductivity. Glycerol has been widely reported to be a fruitful plasticizer in Starch based films. Recent report made by Tiwari et al. has established that Glutaraldehyde is not only an efficacious crosslinker but also helps in attaining higher conductivity in Starch based films [9].