Black garlic is an elaborated product obtained from fresh garlic (Allium sativum L.) at a controlled high humidity and temperature, which leads to modifications in color, taste, and texture. To clarify the physicochemical changes that occur during the thermal process, this work aimed to evaluate and contrast the antioxidant capacity and that of other compounds between purple garlic ecotype "Purple from Las Pedroñeras" and its black garlic derivative. Our results showed numerous differences between both, because black garlic presented a significant divergence in its volatile profile, a decreased amount of ascorbic acid, an increment in sugar and polyphenol contents, a greater antioxidant capacity, and a different composition of phenolic acids and flavonoids.