Knowledge of the oxidative stability of vegetable oils for lubricant applications is a key point, because vegetable oil oxidation potential is the main disadvantage for its use as a lubricant. Oil degradation after an oxidation process can seriously affect its lubricating function and increase wear. In this work, two different methods for evaluating the oxidation stability of lubricating vegetable oils, the oxidation onset temperature, characterized through DSC measurements (ASTM E 2009-08), and the pressure drop in the oxygen pressure vessel (ASTM D 942-02), have been used. Additionally, thermogravimetric analysis and FTIR studies have also been carried out. High-oleic sunflower (HOSO) and castor (CO) oils were selected and blended with natural ((+)-α-tocopherol (TCP), propyl gallate (PG), l-ascorbic acid 6-palmitate (AP)) or synthetic antioxidants (4,4'-methylenebis(2,6-di-tert-butylphenol) (MBP)), with the aim of formulating biodegradable vegetable-based lubricants according to REACH regulation. (1) The results showed that the most effective biodegradable antioxidant is PG, comparable to MBP, whereas lower effectiveness was obtained for TCP and AP. In relation to the methods tested, DSC measurements achieve accurate data more quickly for evaluating the oxidation stability of these basestocks, showing a linear correlation with the traditional method based on the oxygen bomb test. The empirical equation obtained depends on the mechanism involved in the antioxidant activity.