Of current interest in our laboratory is the nature of photoinduced processes in the cavities of zeolites completely submerged in polar solvents, or polar-solvated zeolites (PSZ). The present study addresses the nature of electron trapping in PSZ with emphasis on the zeolites NaX and NaY. Free electrons were generated by two-photon, pulsed-laser excitation of either pyrene or naphthalene included in zeolite cavities. Trapped electrons were monitored by diffuse transmittance, transient absorption spectroscopy at visible wavelengths. In anhydrous alcohols, electron trapping by Na-4(4+) ion clusters was observed in both NaX and NaY. The resulting trapped electrons decayed over the course of tens of milliseconds. No evidence for alcohol-solvated electrons was found. More varied results were observed in solvents containing water. In NaX submerged in CH3OH containing 5% or higher water, species having microsecond lifetimes characteristic of solvated electrons were observed. By contrast, a 2 h exposure of NaY to 95/5 CH3OH/H2O had no effect on electron trapping relative to anhydrous CH3OH. The difference between NaX and NaY was explained by how fast water migrates into the sodalite cage. Prolonged exposure to water at room temperature or exposure to water at elevated temperatures was necessary to place water in the sodalite cages of NaY and deactivate Na-4(4+) as an electron trap. Additional studies in NaY revealed that solvent clusters eventually become lower energy traps than Na-4(4+) as the water content in methanol increases. In acetonitrile-water mixtures, electron trapping by Na-4(4+) was eliminated and no equivalent species characteristic of solvated electrons in methanol-water mixtures was observed. This result was explained by the formation of low energy solvated electrons which cannot be observed in the visible region of the spectrum. Measurements of the rate Of O-2 quenching in anhydrous solvents revealed rate constants for the quenching of ion cluster trapped electrons that were 2-4 times higher than that for pyrene triplets. In NaX, the rate constant in methanol was 10(4) times smaller than that in cyclohexane, showing greater inhibition Of O-2 reactivity in the medium of PSZ. The results of this study point out the conditions under which Na-4(4+) is active as an electron trap in PSZ and that water must be present in the sodalite cage to produce solvated electrons in the supercage.