This investigation assessed the phenolic composition, and the in vitro and in silico antioxidant potential of peels from six potato varieties (Arizona, Spunta, Fabula, Manito, Argos, and Touareg) cultivated in Algeria. 80% ethanol was applied to macerate potato peels, and standard procedures were followed for phytochemical analyses. The in vitro antioxidant capacity was evaluated by the scavenging methods of DPPH (1,1-diphenyl-2-picrylhydrazil) and ABTS ((2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid)) radicals. AutoDock Vina was employed to perform molecular docking analyses. LC–MS/MS analyses revealed significant variability in phenolic compounds among the varieties, with chlorogenic acid being the predominant compound, reaching the highest concentration in Touareg peels (51.28 µg/g). The Manito variety exhibited the highest total phenolic and flavonoids contents of 643.53 ± 2.59 mg GAE/100 g DW and 144.42 ± 2.40 mg QE/100 g DW, respectively and the strongest ABTS radical scavenging activity (IC₅₀ = 473.81 ± 1.35 µg/mL). Molecular docking analysis suggested potential interactions of catechin and chlorogenic acid with oxidative stress-related enzymes namely myeloperoxidase, xanthine oxidase, and 5-lipoxygenase, providing complementary insights into their possible biological relevance. The integration of in vitro and in silico results demonstrates that the Manito variety is the most promising candidate for the sustainable valorization of potato peels as a natural source of antioxidants.