Electron solvation dynamics in photoexcited anion clusters of l(-)(D2O)(n=4-6) and I-(H2O)(4-6) were probed by using femtosecond photoelectron spectroscopy (FPES). An ultrafast pump pulse excited the anion to the cluster analog of the charge-transfer-to-solvent state seen for I- in aqueous solution. Evolution of this state was monitored by time-resolved photoelectron spectroscopy using an ultrafast probe pulse. The excited n = 4 clusters showed simple population decay, but in the n = 5 and 6 clusters the solvent molecules rearranged to stabilize and localize the excess electron, showing characteristics associated with electron solvation dynamics in bulk water. Comparison of the FPES of I-(D2O)(n) with I-(H2O)(n) indicates more rapid solvation in the H2O clusters.