Inter- and intramolecular vibrations of the Phenol dimer have been examined using spectral hole burning and dispersed fluorescence spectroscopy. The dispersed fluorescence spectra have been recorded via excitation of the electronic donor origin and all intermolecular vibrational transitions. The Franck-Condon intensity pattern allowed a straightforward assignment of the ground state vibrational frequencies to the excited state frequencies, which were examined by hole-burning spectroscopy. The existence of another conformer that possibly absorbs in the region of interest was ruled out by hole-burning spectroscopy. For obtaining the hole-burning spectra, the electronic origin of the donor chromophore was analyzed, while the hole-burning laser was scanned over the region of interest. As both acceptor and donor part belong to one molecule the hole-burning signal could be analyzed via fluorescence from one of the chromophores.