Ground-state infrared spectra of the syn and anti conformers of jet-cooled 5-hydroxytropolone (5-HOTrOH) monomer have been recorded free from interference from one another using a fluorescence depletion method. The 5-hydroxy group "free" O-H stretch, 2-hydroxy intramolecularly hydrogen-bonded O-H stretch, and C-H stretch transitions are observed for both conformers. The assignment of these bands is clear by comparison with previous infrared studies of bare tropolone and is confirmed by MP2 and DFT level vibrational frequency and intensity calculations. Each of the conformers is predicted to have four allowed C-H stretch transitions. There is a reasonable one-for-one correspondence between calculation and experiment for the anti conformer’s C-H stretch bands, while the syn conformer shows effects of Fermi resonance mixing. The 5-OH stretch bands of the syn and anti conformers are single, sharp transitions located at 3654 and 3664 cm(-1), respectively. The OH stretch fundamentals of the 2-OH group involved in the intramolecular hydrogen bond are centered on 3170 and 3195 cm(-1). These bands are extensively broadened in both conformers and contain reproducible substructure with irregular spacing of about 10-15 cm(-1). The substructure of the intramolecularly H-bonded 2-hydroxy O-H stretch band reflects a selective first-tier vibrational-state mixing, most likely with a set of modes which are in near two-to-one resonance with it. Finally, the 249 cm(-1) asymmetry in the double-minimum potential well for H atom tunneling appears to be sufficient to quench syn-anti tunneling in S-0 even following excitation of the 2-OH stretch fundamental. No evidence is found for syn <----> anti "crossover" transitions despite careful searches capable of detecting such transitions at depletion levels of about 1%.