The laser-induced fluorescence spectra of jet-cooled benzo-18-crown-6 (B18C6) and dibenzo-18-crown-6 (DB18C6) exhibit a number of vibronic bands in the 35000–37000 cm−1 region. We attribute these bands to monomers and hydrated clusters by fluorescence-detected IR-UV and UV-UV double resonance spectroscopy. We found four and two conformers for bare B18C6 and DB18C6, and the hydration of one water molecule reduces the number of isomers to three and one for B18C6-(H2O)1 and DB18C6-(H2O)1, respectively. The IR-UV spectra of B18C6-(H2O)1 and DB18C6-(H2O)1 suggest that all isomers of the monohydrated clusters have a double proton-donor type (bidentate) hydration. That is, the water molecule is bonded to B18C6 or DB18C6 via two O–H・・・O hydrogen bonds. The blue shift of the electronic origin of the monohydrated clusters and the quantum chemical calculation suggest that the water molecule in B18C6-(H2O)1 and DB18C6-(H2O)1 prefers to be bonded to the ether oxygen atoms near the benzene ring.