Despite a large number of previous studies, the mechanism of free radical interaction between vitamin E (VE) (alpha-, beta-, gamma- and delta-tocopherol) and ascorbate or flavonoids as coantioxidants remains unclear. VE, particularly alpha-tocopherol, shows less antioxidant activity against peroxyl radicals, suggesting that VE possesses functions that are independent of its antioxidant/radical-scavenging activity. The synergistic antioxidant effect of VE or L-ascorbyl 2,6-dibutyrate (ASDB, an ascorbate derivative) with the flavonoids (-)-epicatechin (EC) and (-)-epigallocatechin gallate (EGCG) was investigated using the induction period method in the polymerization of methyl methacrylate initiated by thermal decomposition of benzoyl peroxide (an oxygen-centered radical, PhCOO*) under nearly anaerobic conditions. For delta-tocopherol, a synergistic antioxidant effect was observed in the presence of both EC and EGCG, whereas antioxidant activity for alpha-, beta- and gamma-tocopherol was decreased by addition of EC and EGCG. This suggested that the partial regeneration between VE and flavonoids may depend on the chemical structure of VE, i.e., monomethyl, dimethyl, or trimethyl tocol. The regeneration of delta-tocopherol, a monomethyl tocol, by flavonoids may be due to the lower steric effect of tocol. For ASDB, regeneration of vitamin E, which is well-known for a VE/ascorbate mixture, was not observed, possibly due to the anaerobic experimental conditions. The radical interaction between VE and EC, EGCG or ASDB suggests reactivity of VE with biological systems.