Starchy materials are extracted from five Andean native potato varieties—Yana Puma Maqui (YP), Yana Winku (YW), Mulu Mata (MM), Qeqorani (Q), and Kuchi Aqcha (KA)—and characterized. Edible films from potato starchy materials are then produced and characterized. The YP and YW starchy materials show better antioxidant activity. The YP starchy material presents the largest particle size, the lowest starch content, and the highest amylose content, which decreases its swelling power and prevents granules from being disrupted at high temperatures. The YP starchy material films have high mechanical strength, but they are the most hydrophilic. The KA starchy material yields a gel with greater clarity and less tendency to retrograde. Because of its high amylopectin content, its films are more elongatable and less hydrophilic and have the lowest mechanical strength. The MM starchy material presents the smallest particle size, which increases its thermal stability and decreases its swelling power and amylose leaching. This starchy material yields a less soluble gel with less clarity at 25, 4, and −18 °C, and its films are the most elongatable. Meanwhile, the YW starchy material has the greatest swelling power, which results in thicker films with better mechanical properties and water resistance.