The use of alternatives for petroleum-based products is becoming more and more important, especially considering the new and constantly changing geopolitical context, where excessive energy dependence is not desirable. Thus, biodiesel could play an important role in contributing to the implementation of biorefineries, which represent desirable goals in terms of sustainability, green chemistry and the circular economy. However, one challenge related to biodiesel based on vegetable oils is its low oxidative stability, which can alter the properties of these products during storage. To avoid this problem, interesting antioxidants, such as propyl gallate (PG), could be added to biodiesel to allow it to keep its main properties during oxidation. Additionally, monitoring PG content during oxidation is interesting, and the use of voltammetry could be suitable for this purpose. The aim of this work was to assess the effectiveness of PG during cardoon biodiesel oxidation, while monitoring the process through cyclic voltammetry (CV). As a result, it was proven that PG was highly effective, increasing the length of oxidative stability to more than 10 h at low concentrations (600 mg·L−1) and retaining its main properties (viscosity and acidity) during oxidation. Regarding CV, this technique was successfully optimized to determine PG concentration in cardoon biodiesel during oxidation.