This work examined concentration-dependent variations in the fluorescence spectra of solutions of perylene and PMMA in toluene during the process of evaporation, using fluorescence microscopy. At low perylene concentrations, the fluorescence spectra of the resulting perylene/PMMA films exhibited a structural band originating from monomeric perylene. Increasing the concentration resulted in the appearance of new, broader bands due to the formation of two excimer species. An estimation of variations in the fluorescence excitation spectra of these same films with changing concentration and excitation wavelength indicated the formation from monomer to fully overlapped excimer via partially overlapped excimer in terms of the kinetic situation. These species are believed to consist of either ground state aggregates or alpha-crystals resulting from phase separation within the PMMA films. Dynamic fluorescence changes during solvent evaporation were monitored by fluorescence spectroscopy and CCD photography. Fluorescence emission changed from blue to green with the formation of alpha-crystals, a pattern which was also observed when increasing perylene concentrations in PMMA films during static trials. The concentration distribution around a-crystals was attributed to the crystal growth process and could be followed by observing the fluorescence color gradient radiating from the crystal. Studying concentration-dependent fluorescence spectral changes during solvent evaporation not only provides insight into the molecular dynamics of the casting process and the compatibility between the dispersed material and the polymer matrix but also provides information concerning molecular assembly and the nucleation and growth of crystals of the fluorescent organic molecules.