Ionic liquids (ILs) have received attention for many years due to them being very promising as green solvent substitutes, but they are not fully understood, especially their behavior dissolved in other solvents, for example, water. Thus, the goal of this contribution is to show insight into the different IL-water mixtures interaction. In this way, two protic ILs (PILs), ethylammonium nitrate (EAN) and 1-methylimidazolium acetate (MIA), mixed with water were investigated. To study the PILs-water interaction, the unique spectroscopical behavior in water of the molecular probe 4-aminophthalimide (4-AP) was used. 4-AP emission spectra show hypsochromic shifting by changing the excitation wavelength and, using time-resolved spectroscopy, can be detected by a blue shifting with time. Also, the water mixture of an aprotic IL, 1-methyl-3-butylimidazolium tetrafluoroborate (bmimBF4), and three alcohols, methanol (MeOH), 2-propanol (2-PrOH), and t-butanol (t-BOH), were investigated for comparison. Our results show that the water-ILs interaction is dominated by the size of the IL components, in particular, the cation size. Thus, in MIA-water and bmimBF4-water mixtures, 4-AP is mostly solvated by the IL, even at a low IL molar fraction, as in the t-BOH-water mixture. This finding is especially interesting when ILs-water mixtures are used as a solvent in an organic reaction, where it may call attention to water probably not being the solvent that is interacting with the reactants.