Purple potato is one of the least known and consumed potato varieties. It is as rich in nutrients, amino acids and starches as the rest of the potato varieties, but it also exhibits a high content of anthocyanins, which confer it with some attractive health-related properties, such as antioxidant, pain-relieving, anti-inflammatory and other promising properties regarding the treatment of certain diseases. A novel methodology based on ultrasound-assisted extraction has been optimized to achieve greater yields of anthocyanins. Optimal extraction values have been established at 70 °C using 20 mL of a 60% MeOH:H2O solution, with a pH of 2.90 and a 0.5 s−1 cycle length at 70% of the maximum amplitude for 15 min. The repeatability and intermediate precision of the extraction method have been proven by its relative standard deviation (RSD) below 5%. The method has been tested on Vitelotte, Double Fun, Highland and Violet Queen potatoes and has demonstrated its suitability for the extraction and quantification of the anthocyanins found in these potato varieties, which exhibit notable content differences. Finally, the antioxidant capacity of these potato varieties has been determined by means of 2,2-diphenyl-1-picrylhydrazyl (DDPH) radical scavenging and the values obtained were similar to those previously reported in the literature.