The oxidative stability of refined sunflower oil in the presence and in the absence of propyl caffeate (PC), propyl hydrocaffeate (PHC), propyl ferulate (PF), and propyl isoferulate (PI) has been evaluated according to the Rancimat method. The antioxidant activity of the phenolic derivatives was compared with that obtained with native [alpha-tocopherol (alpha-TOH)] and synthetic [propyl gallate (PG)] antioxidants. The results allow the establishment of a decreasing order of antioxidant power: PG > PHC > PC >> alpha-TOH > PI > PF. The oxidative stability was improved neither by the addition of PF nor by a supplement of alpha-TOH. Moreover, a positive antioxidant effect was obtained for PC that was placed between those of alpha-TOH and PG. The antioxidant activity of PHC was higher than that of its analogue (PC). A dose-dependent effect was observed for PG, PHC, and PC. A chain-breaking mechanism was proposed for the antioxidant activity of propyl phenolic esters because the same ranking order of efficacy was obtained for their antiradical activities evaluated by using the 2,2-diphenyl-1-picrylhydrazyl radical method.