Summary Plant leaf temperatures can differ from ambient air temperatures. A temperature gradient in a gas mixture gives rise to a phenomenon known as thermodiffusion, which operates in addition to ordinary diffusion. Whilst transpiration is generally understood to be driven solely by the ordinary diffusion of water vapour along a concentration gradient, we consider the implications of thermodiffusion for transpiration. We develop a new modelling framework that introduces the effects of thermodiffusion on the transpiration rate, E. By applying this framework, we quantify the proportion of E attributable to thermodiffusion for a set of physiological and environmental conditions, varied over a wide range. Thermodiffusion is found to be most significant (in some cases > 30% of E) when a leaf‐to‐air temperature difference coincides with a relatively small water vapour concentration difference across the boundary layer; a boundary layer conductance that is large as compared to the stomatal conductance; or a relatively low transpiration rate. Thermodiffusion also alters the conditions required for the onset of reverse transpiration, and the rate at which this water vapour uptake occurs.