In this paper, the excited state dynamics properties of hemicynine were investigated by using time-resolved fluorescence and 3D fluorescence spectra techniques. The interaction of hemicyanine molecules caused formation of H-aggregates and a blue shift of the 3D fluorescence spectra in interleaving hemicyanine/arachidic acid multilayers. The peak of fluorescence was a red shift along with the time decay. The lifetime of the LB fluorescence was much shorter and the difference of beginning luminescence was less than that of the hemicyanine solution due to the stronger intermolecule interactions in the aggregates.