Hemicyanine Langmuir–Blodgett films have been elaborated and characterized using stationary and time-resolved spectroscopic techniques. Depending on the experimental conditions, especially the pH of the water subphase, the absorption spectra of the films indicate the presence of non-fluorescent Haggregates in the monolayer. Time-resolved fluorescence measurements revealed three mono-exponential decay times: a very short one (20–23 ps) attributed to an excited intramolecular charge transfer state and two longer ones (100–120 ps and 400–590 ps) attributed to thephotoisomerization of the chromophores.