Alkylresorcinols are a group of natural phenolic compounds found in various foods such as whole grain cereals, bread, and certain fruits. They are known for their beneficial health effects, such as anti-inflammatory and anti-cancer properties. This study aimed to evaluate the antioxidant activity of two typical alkylresorcinols namely olivetol and olivetolic acid (Oli and OliA) under physiological conditions. The free radical scavenging capacity of Oli and OliA toward oxygenated free radicals (HO˙ and HOO˙ radicals) was investigated using thermodynamic and kinetic calculations. The results revealed that Oli and OliA are potent scavengers of HO˙ radical in both polar and lipid media, acting exclusively via the FHT (formal hydrogen transfer) mechanism. Moreover, they demonstrated excellent scavenging activity toward HOO˙ radical in water via the SET (single electron transfer) mechanism, outperforming the common antioxidant BHT. In lipid media, Oli and OliA showed moderate scavenging activity toward HOO˙ radical via the FHT mechanism. Significant prooxidant potential of OliA- was also demonstrated through the formation of complexes with copper ions. Additionally, docking studies indicate that the compounds exhibited a good affinity for ROS-producing enzymes, including myeloperoxidase (MP), cytochrome P450 (CP450), lipoxygenase (LOX), and xanthine oxidase (XO), highlighting their potential as natural antioxidants with promising therapeutic applications.