Upon photoexcitation of iodide-methanol clusters, I-(CH3OH)(n), to a charge-transfer-to-solvent (CTTS) excited state, extensive relaxation was found to occur, accompanied by a convoluted modulation of the stability of the excited electron, which ultimately decreases substantially. In order to develop a molecular-level understanding of the relaxation processes of CTTS excited I-(CH3OH)(n), high-level quantum chemical calculations are first used to investigate the ground, excited, and ionized states of I-(CH3OH)(n) (n = 2). Because of the relatively small size of I-(CH3OH)(2), it was possible to characterize the contributions of solvent-solvent interactions to the stability of the CTTS excited cluster relative to dissociation into methanol, iodine, and a free electron, which exhibits a substantial dependence on the cluster geometric configuration. Ab initio molecular dynamics simulations of CTTS excited I-(CH3OH)(3) are then performed to shed some light onto the nature of the relaxation pathways involved in the modulation of the stability of the excited electron in larger clusters. Simulation results suggest that separation of I and (CH3OH)(3)(-) accompanied by solvent reorganization in the latter can initially stabilize the excited electron, while gradual cluster fragmentation to 1, (CH3OH)(2)(-), and CH3OH ultimately destabilizes it. This work shows, for the first time, that the inability of small CTTS excited I-(CH3OH)(n) to retain a solvated electron may be attributed to the limited hydrogen-bonding capacity of CH3OH, which increases the propensity for fragmentation to smaller clusters with lower excess-electron binding energies, and highlights the critical role of intricate molecular interactions in the electron solvation process.