Antioxidant regeneration could be influenced by various factors such as antioxidant locations and pH conditions. The effects of environmental pH on the antioxidant interaction between rosmarinic acid and α-tocopherol in oil-in-water (O/W) emulsions were investigated. Results showed that the combined antioxidants at pH 7 exhibited the strongest synergistic antioxidant activity in comparison with the combinations at other pH conditions as indicated by the interaction index. A drop in pH from 7 to 3 resulted in a reduction in the synergistic effect. However, in the case of pH 3, an additive effect was obtained. Moreover, the effect of the pH on the regeneration of α-tocopherol by rosmarinic acid in heterogeneous Tween 20 solutions was studied using EPR spectrometer. The same was true for the regeneration efficiency, where the reaction at pH 7 exhibited the highest regeneration efficiency of 0.3 mol of α-tocopheroxyl radicals reduced/mol of phenolics. However, the study on depletions of rosmarinic acid and α-tocopherol revealed that the formation of caffeic acid, an oxidative degradation product of rosmarinic acid, could be involved in enhancing the antioxidant activity observed at pH 7 rather than the antioxidant regeneration. This study has highlighted that the importance of pH-dependent antioxidant interactions does not solely rely on antioxidant regeneration. In addition, the formation of other oxidative products from an antioxidant should be taken into account.