The photoinduced electron transfer from eosin, Eo(2-) (1), and ethyl eosin, EoEt(-) (2), to Fe(CN)(6)(3-) is examined in AOT reverse micelles in heptane. For a microheterogeneous system having a water-to-surfactant molar ratio w = 30, the lifetime of the photogenerated redox products in the system that includes EoEt(-) is ca. 300-fold longer than in the photosystem that includes Eo(2-) : tau = 4.3 mu s for Eo(2-) and tau = 1400 mu s for EoEt(-). Stabilization of the redox products against recombination in the system containing EoEt(-) is attributed to the extraction of the hydrophobic oxidized photoproduct (2)EoEt(.) from the water pool of the reverse micelles to the continuous oil phase. Photoinduced electron transfer from Eo(2-) to Fe(CN)(6)(3-) in the reverse micelles has been quantitatively analyzed by assuming a Poisson distribution of the quencher over the reverse micelles. Kinetic analysis of the transients allowed determination of the quencher distribution, micelle concentration [m] 1.44 x 10(-4) M, and water-pool diameter 2R = 82 Angstrom. The kinetics of photoinduced electron transfer from EoEt(-) to Fe(CN)(6)(3-) could be analyzed in terms of a similar quencher distribution. Detailed kinetic analysis revealed that, in the Eo(2-)/Fe(CN)(6)(3-) reverse-micellar photosystem, photoinduced electron transfer is followed by a fast intramicellar recombination. In the EoEt(-)/Fe(CN)(6)(3-) photosystem, fast escape of the neutral oxidized species (2)EoEt(.) from the reverse micelle competes with the intramicellar recombination (escape efficiency : theta(esc) = 0.52), leading to separation of the redox products. The separated photoproducts undergo a slow secondary recombination. A kinetic model for the overall photochemical processes is presented, and kinetic equations for the photoinduced electron transfer in the reverse micelles followed by intramicellar recombination and escape are provided.