Hydrogen-bonded complexes of the photoacid 1-naphthol with NH3 and ND3 were investigated by resonant two-photon ionization, spectral hole burning, and fluorescence spectroscopies. Although the intermolecular vibrations are weak in both absorption and emission, with typical Franck–Condon factors <2% relative to the electronic origin, all six intermolecular modes were identified, namely the hydrogen bond stretch σ, the ammonia torsion τ, two in-plane wags β1 and β2, and two out-of-plane rocking motions ρ1 and ρ2. Several ammonia torsional excitations were observed, with spacings in good agreement with the S0- and S1 state effective torsional barriers derived by Humphrey and Pratt [J. Chem. Phys. 104, 8332 (1996)]. The β1, β2, and ρ2 vibrational excitations exhibit large (2–8 cm−1) torsional splittings, which indicate strong anharmonic coupling with the ammonia internal rotation. The observed Franck–Condon factors of the intermolecular stretching vibration imply a contraction of the O–H⋅⋅⋅N hydrogen bond by ≈0.01 Å upon S1←S0 excitation.