A study of the vibrational bands of the red-most pigments in the minor photosystem II antenna protein, Lhcb4, is presented. The two vibrational techniques used, resonance Raman and fluorescence line-narrowing (FLN) spectroscopies, are shown to give essentially the same information on the pigments investigated, with the exception that FLN provides information on the red-most, fluorescence-emitting species only. Fluorescence emission at 4.2 K is shown to originate from two pools of chlorophylls one of which, contributing to 50% of the emission, corresponds to only one chlorophyll molecule per monomer. This opens the way to the identification of the emitting species within the three-dimensional model of Lhcb4.