The properties of chlorophyll (Chl) a and pheophytin (Pheo) a embedded in the rigid anhydrous polymer fihns, polyvinyl alcohol (PVA) and nitrocellulose (NC) are reviewed. The aggregation capability of these pigments in two matrices is characterized by absorption, fluorescence, excitation spectra combined with fluorescence lifetime and time-resolved anisotropy. The dimer creation ability for Chl a and Pheo a is strongly affected by the polymer systém ušed for investigation. The Chl a and Pheo a ability to aggregate in polymer matrices is compared. We háve been looking for a good systém suitable for the study of properties of monomeric forms when embedded in the rigid matrix on the one hand, and for the study of energy transfer between different forms of Chl molecules on the other one. Chl a, when embedded in an anhydrous PVA matrix, is in a very stable monomeric form while Pheo a molecules in this film tend to aggregate and in the NC film they exist in the monomeric form. Thus the PVA systém can be ušed as a model systém for investigation of the properties of and processes between both dimeric and monomeric structures. The NC film, however, can be ušed as a rigid matrix when only the existence of monomeric forms of the pigments is required.