Development of an antioxidant assay explaining antioxidant behaviors in complex food systems has been a challenging topic for food scientists. This research aimed to investigate antioxidant capacities and interactions of selected synthetic antioxidants and commercial natural antioxidant extracts using the CAT assay and a newly developed ApoCAT assay, which used water- and lipid-soluble azo radical initiators, respectively. Results suggested that the higher the hydrophobicity of an antioxidant, the higher the antioxidant capacity of an antioxidant observed in the ApoCAT assay. The relationship between the two different assays was explained by the ratio between the ApoCAT and the CAT values. Interestingly, all lipophilic derivatives of the antioxidants exhibited higher ApoCAT/CAT ratios than their hydrophilic derivatives. In the case of the commercial food-grade antioxidants, green tea extract and mixed tocopherols showed a higher antioxidant capacity in the ApoCAT assay than in the CAT assay, while grape seed and rosemary extracts did not show significantly different changes in behaviors in both assays. The study on antioxidant interactions revealed that additive, synergistic, and antagonistic effects between hydrophilic antioxidants and natural extracts, and mixed tocopherols could be observed in both the CAT and the ApoCAT assays, depending on the combined ratios. In most cases, at a particular ratio, the synergistic effect reached the maximum level before suddenly dropping to additive and antagonistic effects in both assays.