We have conducted time-resolved experiments (pump-probe and pump-repump-probe) on a model aromatic chromophore, aniline, after excitation in water at 267 nm. In the initial spectra recorded, in addition to the absorption corresponding to the bright pp* excitation, the fingerprint of a transient state with the electron located on the solvent molecule is identified. We postulate that the latter corresponds to the ps* state along the N-H bond, whose complete relaxation with a similar to 500 ps lifetime results in the formation of the fully solvated electron and cation. This ionization process occurs in parallel with the pp* photophysical channel that yields the characteristic similar to 1 ns fluorescence lifetime. The observed branched pathway is rationalized in terms of the different H-bonds that the water establishes with the amino group. The proposed mechanism could be common for aromatics in water containing N-H or O-H bonds and would allow the formation of separated charges after excitation at the threshold of their electronic absorptions.