Background: Olive pomace, a byproduct of olive oil production, represents approximately 85% of the processed material and poses environmental risks when improperly discarded. Its composition is rich in polyphenols with potential for cosmetic use, especially in skin barrier care. Objective: To develop a natural extract rich in antioxidants from olive pomace using sustainable solvents (water and 1,3-propanediol) for skin barrier support. Methods: The phenolic composition and in vitro biological activities of the extracts were analyzed. Results: The extracts demonstrated a reducing capacity (15 to 33 mg GAE/g) and flavonoid content (4 to 5 mg QE/g). In addition, their antioxidant capacity was proven through the inhibition of the DPPH radical (7% to 91%) and ABTS (7% to 95%) and the reduction in oxidation in the beta-carotene/linoleic acid system (6% to 35%), presenting results superior to those of tocopherol acetate. The hydroxytyrosol and oleuropein compounds, ranging from 28 to 54 and 51 to 85 µg/mL, respectively, were quantified via HPLC. The extract with the highest levels of hydroxytyrosol and oleuropein was analyzed via UHPLC-QqTOF-MS, and 33 compounds were identified. This extract showed antiglycation activity (24% to 40%). The incorporation of this extract into a cosmetic emulsion resulted in sufficient antioxidant capacity to replace tocopherol acetate. Conclusions: The use of effective extraction techniques and nontoxic solvents ensures the sustainability and safety of the extract for application as a natural cosmetic ingredient, aiming to promote the health and integrity of the skin barrier.