2-naphthyl-1-ethanol/(water)2 and 2-naphthyl-1-ethanol/(methanol)2 complexes have been formed in a supersonic expansion and studied by laser induced fluorescence (LIF) and IR/UV double resonance spectroscopy in the region of the O–H stretch. Comparison of the measured frequencies with DFT calculations has led to the attribution of the observed 2-naphthyl-1-ethanol/(water)2 and 2-naphthyl-1-ethanol/(methanol)2 complexes to bridged structures. In these structures the solvent dimer is inserted in between the OH group of the chromophore which acts as a hydrogen bond donor, and the electron π system of the aromatic ring. Electronic excitation results in a red shift of all the νOH stretch frequencies.