In order to reduce our dependence on nonrenewable plastics and solve the problem of non-biodegradable plastic waste, there has been much attention paid to the development of biodegradable plastics from natural resources. Starch-based materials have been widely studied and developed for commercial production, primarily from corn and tapioca. However, the use of these starches could generate food security problems. Therefore, the use of alternative starch sources, such as agricultural waste, would be of great interest. In this work, we investigated the properties of films prepared from pineapple stem starch, which has a high amylose content. Pineapple stem starch (PSS) films and glycerol-plasticized PSS films were prepared and characterized using X-ray diffraction and water contact angle measurements. All films exhibited some degree of crystallinity, making them water-resistant. The effect of glycerol content on mechanical properties and gas (oxygen, carbon dioxide and water vapor) transmission rates was also studied. The tensile modulus and tensile strength of the films decreased with increasing glycerol content, while gas transmission rates increased. Preliminary studies showed that coatings made from PSS films could slow down the ripening process of bananas and extend their shelf life.