In this paper an ab initio theoretical study of the precursors of the charge-transfer-to-solvent (CTTS) states in I-(H2O)(n) clusters is presented. While there is no bound excited state in monohydrated iodide I-(H2O), the CTTS precursor states, denoted as I-(H2O)(n)*, emerge at cluster size n greater than or equal to 2, which confirms a recent experimental observation [Serxner et al. J. Chem. Phys. 1996, 105, 7231.]. In addition, two or more bound excited states are found for larger clusters. The absorption maximum of the interior structure of I-(H2O)(6) is found to be 5.02 eV, comparable to the experimental value of 5.48 eV found in the bulk, indicating that the first hydration shell of the aqueous halide makes a very significant contribution to the solvation energy of the lowest CTTS state and that the molecular details of solvent molecules play an important role in forming the CTTS states. Comparing the CTTS precursor states I-(H2O)(n)* with the electronic states of the corresponding water cluster anions, e(-)(H2O)(n), shows that the excited electron distributions are excluded from the region occupied by the electrons of the iodine atom, which in turn results in higher energies for I-(H2O)(n)* compared with e(-)(H2O)(n). Moreover, it is shown that the cluster size dependence and isomer specificity of the excitation energies and absorption intensities of the I-(H2O)(n) clusters may provide a diagnostic tool in determining the predominate structure, surface or interior, of I-(H2O)(6).