A report is given of the results of investigations of electronic-vibrational spectra of chlorophyll molecules and their analogs, embedded in solid-state matrices, which were carried out using modern selective spectroscopic methods such as laser monochromatic excitation of the fluorescence and spectral hole burning. The fundamentals of the application of these methods to complex impurity molecules are considered together with the problems encountered in the analysis of the structure of the selective spectra, mechanisms of the appearance of stable and dynamic spectral holes, and determination of homogeneous spectral profiles and relaxation times. Special attention is given to a theory of the appearance of zero-phonon lines under energy transfer conditions and experimental detection of these lines in model and native systems.