Resonant two-photon ionization (R2PI) and fluorescence spectra of the 1-naphthol . H2O and 1-naphthol-d(1) . D2O cluster are reported and interpreted with emphasis on intracomplex vibrational energy redistribution (IVR) and vibronic coupling. The analysis included an ab initio normal-coordinate calculation of both complexes at the 6-31G (d,p) level. In S-1 <-- S-0 R2PI spectra, the intermolecular modes were found to be very weak; only one such Si vibration was observed at 57 cm(-1) (54 cm(-1) for 1-naphthol-OD . D2O). At excitations less than 400 cm(-1) above the S-1 <-- S-0 origin, the fluorescence spectra retain a simple 1-naphthol-like pattern. At higher excess energies, the fluorescence exhibits complex structure due to emission from both relaxed and unrelaxed S-1 vibrational states, showing efficient coupling through the hydrogen bond. This restricted IVR behavior changes to dissipative IVR at about 834 cm(-1) above the S-1 <-- S-0 origin. Exceptions to general IVR are observed. The S-1 + 403 cm(-1) level is a restricted IVR case, while the nearby S-1 + 400 cm(-1) level undergoes nearly dissipative IVR. On the other hand, a nearly "frozen" mode is observed at 553 cm(-1) above the S-1 <-- S-0 origin. By use of the ab initio vibrational analysis and lowest-order anharmonic coupling, the IVR-active vibrational "bath" states can be predicted, enabling tentative assignment of much of the relaxed fluorescence structure. Ion-dip spectroscopy shows that IVR in the electronic ground state may have a higher onset threshold than in the S-1 by greater than or equal to 130 cm(-1). Exciting one quantum of the 57 cm(-1) intermolecular mode results in a decreased SO IVR threshold. The strong vibronic S-1-S-2 coupling earlier observed for vibrations at S-1 + 410 and S-1 + 414 cm(-1) in free 1-naphthol was found to be partially inhibited in 1-naphthol . H2O but still significant in 1-naphthol-OD . D2O. This is attributed to harmonic mode mixing. In contrast, vibronic coupling becomes active in the S-1 + 292 cm(-1) level of 1-naphthol . H2O.