Water and methanol associations in ionic liquids (ILs) have been studied by means of FTIR spectroscopy. Spectra at different concentrations of water or methanol in ILs were obtained by means of on-line dilution using a flow injection analysis system. Spectral features in the OH stretching region revealed that most of the water and methanol molecules tended to be isolated from each other and to interact with the anion of the IL via H bonding. By means of two-dimensional correlation spectroscopy, the formation of methanol and water dimers was also detected. Multivariate curve resolution was used to recover pure spectra and concentration profiles of the different species. Methanol dimers form at concentrations higher than 0.8% (w/w) in the three studied ILs, 1-ethyl-3-methylimidazolium tetrafluoroborate (emimBF₄), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF₄), and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF₆). Self-association of water molecules takes place in emimBF₄ and bmimBF₄ at a molar ratio similar to that of methanol molecules; however, water dimers cannot be detected in bmimPF₆, the most hydrophobic IL studied. No evidence was found that bigger water clusters are formed in these ILs at the studied cosolvent concentrations.