The complexation dynamics of radical cations with cyclodextrins (CD) was studied using photophysical techniques. Radical cations of 4-vinylanisole and trans-anethole were formed within α- and β-CD cavities by two-photon photolysis of the respective styrene precursors. Exit of the radical cations from α-CD complexes with 1:1 and 1:2 (guest : CD) stoichiometries and β-CD complexes with 1:1 stoichiometries occurred with lifetimes shorter than 100 ns. Most of the radical cations formed escape from the CD cavities, but a small portion do react with α-CD when this host is present in high concentrations.