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Amphiphilic 4-(3‘,4‘-dimethoxystyryl)-N-octadecylpyridinium perchlorate and bromide form stable monolayers at the air/water interface. Small differences in the surface pressure−area and surface potential−area isotherms depending on the anion indicate interactions between the chromophore and the anions on the pure water subphase. The monolayer behavior is considerably modified on 10 mM aqueous solutions of KI, KClO4, KCl, and KF as revealed by isotherm measurements, reflection spectroscopy, and Brewster angle microscopy. The phase transition observed in the isotherms is shifted to higher surface pressure because of variation of the salt according to the Hofmeister series. Upon monolayer compression, the chromophores are increasingly tilted, and a shift of the band to longer wavelengths is attributed to the environment becoming less polar. However, in the case of KCl at small areas per molecule, relaxation is observed at constant area with the appearance of a new band shifted to shorter wavelengths. This band is assigned to small associates of about four chromophores (H aggregates). In the case of KI, a new band shifted to longer wavelengths is found. Theoretical calculations did not yield a transition in the observed range, even for large aggregates (J aggregates). Therefore, other interactions may be responsible for the appearance of this band.