The effect of water on the hydrophobic ionic liquid (IL) 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonylimide) and its Li+ mixture was evaluated. The electrochemical stability, density, viscosity, and ionic conductivity were measured for both systems in different concentrations of water. The presence of Li+ causes a large increase in the water absorption ability of the IL. The experimental results suggest a break of the interactions between Li+ and Tf2N- anions in the strong aggregates formed in dried Li+ mixtures, modifying the size and physicochemical nature of these aggregates. It is also observed that the size of the ions aggregates with formal charge increases at high temperature and decreases the mobility of the charge carrier, explaining the break in the Walden rules at high temperature. Raman spectroscopy and molecular dynamic simulations show the structural change of these systems. In neat ILs, the water molecules interact mainly among each other, while in the Li+ mixtures, water interacts preferentially with the metallic cation, causing an important change in the aggregates present in this system.