Isotopic exchange with atmospheric vapour can strongly influence the isotopic values of evaporating surface water bodies (e.g., lakes), influencing our understanding of hydrological processes across aquatic and terrestrial environments. Rather than measure the isotopic values of the atmosphere directly, it is much more common to estimate values by assuming equilibrium with local precipitation. This assumption may introduce large errors, thereby biasing hydrological inferences and understanding. The pattern and magnitude of this error has been quantified only in a few circumstances. We compared observations of vapour and precipitation isotope values over a four‐year record collected in a montane environment in the central Rocky Mountains of North America. We further investigated factors and conditions promoting disequilibrium. Scenario comparisons assessed the impact of theoretical and methodological elements on the accuracy of the equilibrium assumption. We found that the equilibrium assumption was not well supported by direct and continuous observations of vapour isotopes using tower‐based laser isotope spectroscopy, particularly during the summer months. Across all scenarios, errors associated with the equilibrium assumption were high, credibly ranging from 14 to 154 ‰ for δ 2H and 1.5 to 16.3 ‰ for δ 18O. Environmental covariates (e.g., vapour pressure deficit, air pressure) helped explain some of the apparent disequilibrium. Although the equilibrium assumption for estimating atmospheric vapour isotope values may not be applicable in a continental montane environment, our findings highlight opportunities for using direct vapour isotope measurements to better understand vapour sources, air mass mixing, and phase changes over complex mountainous terrain, which in turn may better constrain regional‐ to global‐scale hydrological process estimates, such as evapotranspiration rates and the water budgets of mountain lakes.