In micellar solutions, one-electron reduction of O-center dot(2)-radical-anions by 3-alkylpolyhydroxyflavones (FnH) with alkyl chains of n = 1, 4, 6, 10 carbons produces phenoxyl radicals ((center dot)Fn) identical to those obtained by one-electron oxidation by Br-center dot(2)- radical-anions or by repair of tryptophan radicals. In cetyltrimethylammonium bromide (CTAB), FIH localizes in the Stem layer, and alkyl chains of other FnH solubilize in the hydrophobic interior, interacting with cetyl tails. This interaction produces more compact micelles with lower intramicellar fluidity, as suggested by the increase in the pseudo-first-order rate constant of (center dot)Fn formation (k(1)) from similar to 390 s(-1) for n = 1 to 610 s(-1) for n = 10, leading to an intramicellar bimolecular rate constant of 1 x 10(5) M-1 S-1. Additionally, (center dot)F1 and (center dot)F4 decay by intermicellar bimolecular reaction (2k = 20 and 2 x 10(5) M-1 s(-1), respectively) whereas other (center dot)Fn radicals are stable over seconds due to increased localization with regards to the Stern layer. In contrast, the thick uncharged hydrophilic palisade layer and the compact hydrophobic core of Triton X100 micelles are responsible for a much higher microviscosity resulting in a decrease in k(1) from similar to 15.6 s(-1) for n = 1 to 9.6 s(-1) for n = 10.