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High-temperature tolerance in plants is important in a warming world, with extreme heat waves predicted to increase in frequency and duration, potentially leading to lethal heating of leaves. Global patterns of high-temperature tolerance are documented in animals, but generally not in plants, limiting our ability to assess risks associated with climate warming. To assess whether there are global patterns in high-temperature tolerance of leaf metabolism, we quantified T-crit (high temperature where minimal chlorophyll a fluorescence rises rapidly and thus photosystem II is disrupted) and T-max (temperature where leaf respiration in darkness is maximal, beyond which respiratory function rapidly declines) in upper canopy leaves of 218 plant species spanning seven biomes. Mean site-based T-crit values ranged from 41.5 degrees C in the Alaskan arctic to 50.8 degrees C in lowland tropical rainforests of Peruvian Amazon. For T-max, the equivalent values were 51.0 and 60.6 degrees C in the Arctic and Amazon, respectively. T-crit and T-max followed similar biogeographic patterns, increasing linearly (similar to 8 degrees C) from polar to equatorial regions. Such increases in high-temperature tolerance are much less than expected based on the 20 degrees C span in high-temperature extremes across the globe. Moreover, with only modest high-temperature tolerance despite high summer temperature extremes, species in mid-latitude (similar to 20-50 degrees) regions have the narrowest thermal safety margins in upper canopy leaves; these regions are at the greatest risk of damage due to extreme heat-wave events, especially under conditions when leaf temperatures are further elevated by a lack of transpirational cooling. Using predicted heat-wave events for 2050 and accounting for possible thermal acclimation of T-crit and T-max, we also found that these safety margins could shrink in a warmer world, as rising temperatures are likely to exceed thermal tolerance limits. Thus, increasing numbers of species in many biomes may be at risk as heat-wave events become more severe with climate change.