Olive oil and herbs, two key components of the Mediterranean diet, are known for their beneficial effects on humans. In our study, we incorporated aromatic and medicinal herbs into local monovarietal olive oils via maceration procedures for enrichment. We identified the herbal-derived ingredients that migrate to olive oils and contribute positively to their total phenolic content and functional properties, such as radical scavenging activity. Thus, we characterized the essential oil composition of the aromatic herbs (GC-MS), and we determined the phenolic content and antioxidant capacity of the additives and the virgin olive oils before and after enrichment. The herbal phenolic compounds were analyzed by LC-LTQ/Orbitrap HRMS. We found that olive oils infused with Origanum vulgare ssp. hirtum, Rosmarinus officinalis and Salvia triloba obtained an increased phenolic content, by approximately 1.3 to 3.4 times, in comparison with the untreated ones. Infusion with S. triloba led to a significantly higher antioxidant capacity. Rosmarinic acid, as well as phenolic glucosides, identified in the aromatic herbs, were not incorporated into olive oils due to their high polarity. In contrast, phenolic aglycones and diterpenes from R. officinalis and S. triloba migrated to the enriched olive oils, leading to a significant increase in their phenolic content and to an improvement in their free radical scavenging capacity.