Laser induced fluorescence (LIF) excitation spectra of molecular complexes of 1H-pyrrolo[3,2-h]quinoline (PQ) with methanol (n= 1, 2, 3) as well as vibrational spectra of their electronic ground state are reported. The latter have been recorded in the mid-infrared region by fluorescence depletion (FDIR). The only PQ.methanol(n) complex clearly identified in the LIF spectrum is the triply hydrogen-bonded cyclic 1 ratio 2 aggregate. Its stoichiometry has been proven by the femtosecond multiphoton ionization detected infrared measurements [J. Am. Chem. Soc., 2006, 128, 10 000]. The structure of the 1 ratio 2 cluster is determined by means of FDIR spectroscopy in combination with ab initio and DFT calculations. No fluorescence was detected that could be attributed to the 1 ratio 1 cluster. This behaviour of the 1 ratio 1 complex is explained in terms of rapid excited state double proton transfer followed by a non-radiative relaxation. The n= 3 and heavier clusters are fluorescent. Their electronic spectra overlap, preventing the selective measurement of the FDIR spectra of individual complexes.