Extremely heavy precipitation affects human society and the natural environment, and its behaviour under a warming climate needs to be elucidated. Recent studies have demonstrated that observed extreme precipitation increases with surface air temperature (SAT) at approximately the Clausius–Clapeyron (CC) rate, suggesting that atmospheric water vapour content can explain the relationship between extreme precipitation and SAT. However, the relationship between atmospheric water vapour content and SAT is poorly understood due to the lack of reliable observations with sufficient spatial and temporal coverage for statistical analyses. Here, we analyse the relationship between atmospheric water vapour content and SAT using precipitable water vapour (PWV) derived from global positioning system satellites. A super-CC rate appears in hourly PWV when the SAT is below 16 °C, whereas the rate decreases at high SAT, which is different from the precipitation-SAT relationship. The effects of upper air temperature and water vapour can consistently explain the super-CC rate of PWV relative to SAT. The difference between moist and dry adiabatic lapse rates increases with SAT, in consequence of more ability to hold water vapour in the free atmosphere under higher SAT conditions; therefore, attainable PWV increases more rapidly than the CC rate as SAT increases.