The absorption and fluorescence emission spectra of chlorophyll a in different organic solvents where the central Mg atom is either penta- or hexacoordinated have been studied using conventional and selective spectroscopy methods at ambient and cryogenic temperatures. A breakdown of the basic model mirror-symmetry rule in relation to the lowest-energy Qy transitions was observed due to Franck–Condon and Hertzberg–Teller interactions. Detailed vibrational structure in the ground electronic state, virtually independent of the Mg coordination state, was revealed by hole-burning fluorescence line-narrowing technique. The total Huang–Rhys factor associated with the linear vibronic coupling strength of the solvent collective vibrations and the local chlorophyll a intramolecular vibrations is equal to 0.53±0.07 in fluorescence and to 0.39±0.05 in absorption. The electron-phonon coupling part was also found to depend on the excitation wavelength within the inhomogeneously broadened absorption origin band, its average value being Sph≈0.38. All these numbers qualify for the weak vibronic coupling. A comparison of the conjugate Qy absorption and fluorescence emission spectra as well as the temperature dependence of the absorption spectra allowed unambiguous locating of the still controversial Qx absorption band position for penta- and hexacoordinated chlorophyll a species. The basic experimental findings have been qualitatively supported by semiempirical quantum chemical calculations.