Radical cations of several psoralens and coumarins have been generated by photoionization in aqueous micellar solution for a comparison of their dynamic behavior with results observed previously in aqueous solution. The photoionization efficiencies are significantly higher in anionic sodium dodecyl sulfate (SDS) micelles than in aqueous solution as a result of favorable electrostatic effects that lead to rapid ejection of the electron into the aqueous phase. By contrast, much lower quantum yields are measured in neutral and cationic micelles. Experiments with anionic quenchers that are soluble only in the aqueous phase demonstrate that exit of the radical cations from anionic SDS micelles is too slow to measure (< 10(5) s(-1)) under our conditions. Exit rate constants from neutral Triton X-100 micelles are approximately an order of magnitude faster. Comparison of equilibrium constants for both triplet and radical cations of 4,5',8-trimethylpsoralen demonstrates that electrostatic effects lead to an order of magnitude enhancement of the affinity of the radical cation for the anionic vs neutral micelles, as compared to the triplet of the same substrate. The slow exit of the radical cation from the micelle facilitates the measurement of rate constants for reaction of the micelle-incorporated radical cations with both water soluble quenchers and species for which exchange between micelle and aqueous phases is rapid on the time scale of the radical cation lifetime. This work provides some of the first kinetic data for dynamics of exit of reactive radical cations from micelles and indicates that these species may provide useful probes for studying electron-transfer dynamics in micellar media.