In the current work, physicochemical properties of arrowroot starch and thermal properties of glycerol/arrowroot starch membranes were investigated. Arrowroot starch exhibited high purity (starch content >99%) with amylose content >40% and granule size dispersion between 29 and 126 μm. Arrowroot starch has a gelatinization temperature of 63.94°C and a B-type crystalline structure. Arrowroot starch, in combination with three levels of glycerol, was used to manufacture membranes by casting method. Increasing the plasticizer effect due to glycerol content increased the water weight loss of the membranes at temperatures higher than 110°C. Additionally, the onset temperature of the endothermic peak observed by differential scanning calorimetry and associated to water removal from the membranes changed with glycerol content. Physicochemical and thermal properties of arrowroot starch and glycerol/arrowroot starch membranes were similar to those reported previously for other starch sources. From the data obtained in this study, it is clear that arrowroot starch could have promising industrial applications.