Individual vibrational band spectroscopy presents an opportunity to examine Exoplanet atmospheres in detail by distinguishing where the vibrational state populations of molecules differ from the current assumption of a Boltzmann distribution. Here, retrieving vibrational bands of OH in exoplanet atmospheres is explored using the Hot Jupiter WASP-33b as an example. We simulate low-resolution spectroscopic data for observations with the JWST’s NIRSpec instrument and use high resolution observational data obtained from the Subaru InfraRed Doppler instrument (IRD). Vibrational band-specific OH cross section sets are constructed and used in retrievals on the (simulated) low and (real) high resolution data. Low resolution observations are simulated for two WASP-33b emission scenarios: under the assumption of local thermal equilibrium (LTE) and a toy non- LTE model for vibrational excitation of selected bands. We show that the mixing ratios for individual bands can be retrieved with sufficient precision to allow the vibrational population distributions of the forward models to be reconstructed. A simple fit for the Boltzmann distribution in the LTE case shows that the vibrational temperature is recoverable in this manner. For high resolution, cross-correlation applications, we apply the individual vibrational band analysis to an IRD spectrum of WASP-33b, applying an ‘un-peeling’ technique to facilitate the detection. Our results indicate a variation of the cross-correlation signal between two strongest bands of OH consistent with the effective temperature of the WASP-33b atmosphere. We show the feasibility of using this approach to analyse the individual vibrational state populations behind observed and simulated spectra including reconstructing state population distributions.