Soil pH regulates the capacity of soils to store and supply nutrients, and thus contributes substantially to controlling productivity in terrestrial ecosystems 1 . However, soil pH is not an independent regulator of soil fertility-rather, it is ultimately controlled by environmental forcing. In particular, small changes in water balance cause a steep transition from alkaline to acid soils across natural climate gradients 2,3 . Although the processes governing this threshold in soil pH are well understood, the threshold has not been quantified at the global scale, where the influence of climate may be confounded by the effects of topography and mineralogy. Here we evaluate the global relationship between water balance and soil pH by extracting a spatially random sample (n = 20,000) from an extensive compilation of 60,291 soil pH measurements. We show that there is an abrupt transition from alkaline to acid soil pH that occurs at the point where mean annual precipitation begins to exceed mean annual potential evapotranspiration. We evaluate deviations from this global pattern, showing that they may result from seasonality, climate history, erosion and mineralogy. These results demonstrate that climate creates a nonlinear pattern in soil solution chemistry at the global scale; they also reveal conditions under which soils maintain pH out of equilibrium with modern climate.Climate controls many aspects of soil chemistry, affecting soil pH (ref. 4). Alkaline soils are known to be common in arid climates, while acid soils are known to be common in humid climates 1 . Surprisingly, however, the global-scale mechanisms governing this pattern remain broadly defined, and untested by direct observation. What are the dominant chemical equilibria that constrain soil pH? What aspect of climate defines the transition between alkaline and acid soils, and is the transition linear? The answers to these questions are fundamental to understanding soil development and surface geochemistry at the global scale. Furthermore, achieving this understanding may prove essential for representing soils in models of the terrestrial biosphere, given that soil pH controls many aspects of soil fertility 5,6 . Here we illustrate that simple geochemical and hydrological concepts can be used to build a mechanistic understanding of soil pH at the global scale.Interpretations of acid-titration experiments indicate that the soil pH is typically most strongly buffered by equilibrium with two secondary minerals: calcite (CaCO 3 ), or gibbsite (Al(OH) 3 ) 7,8 Fig. 1).Local studies of climate gradients have shown that the relative importance of these two buffers is determined by leaching, which removes Ca 2+ from the soil 2,3,8,9 . In climates where evaporative demand exceeds precipitation, leaching rates are low, and dissolved Ca 2+ accumulates as CaCO 3 -buffering soil pH near 8.2 (ref. 4). Conversely, in climates where precipitation exceeds evaporative demand, water leaches through the soil, removing Ca 2+ and allowing accumulation of relatively immobile...