The lowest electronically excited state of small Na(H2O)(n) clusters has been investigated experimentally and theoretically. The excitation energy as determined by the depletion spectroscopy method drops from 16 950 cm(-1) for the sodium atom down to 9670 cm(-1) when only three water molecules are attached to the Na atom. For larger clusters the absorption band shifts back towards higher energies and reaches 10 880 cm(-1) for n=12. The experimental data are compared to quantum-chemical calculations at the Moeller-Plesset second-order perturbation and multireference single and double excitation configuration interaction levels. We found that the observed size dependence of the transition energy is well reproduced by the interior structure where the sodium atom is surrounded by water molecules. The analysis of the radial charge distribution of the unpaired electron in these interior structures gives a new insight into the formation of the "solvated" electron. (C) 2003 American Institute of Physics.