The effect of high temperatures on CO2 assimilation, metabolite content, and capacity for reducing power production in non-photorespiratory conditions has been assessed in two different bean (Phaseolus vulgarus L.) varieties, Blue Lake (commercially available in the United Kingdom) and Barbucho (a noncommercially bred Chilean variety), which are known to differ in their resistance to extreme high temperatures. Barbucho maintains its photosynthetic functions for a longer period of time under extreme heat compared with Blue Lake. The CO2 assimilation rate was increased by increases in temperature, with a decrease in ratio of rates of temperatures differing by 10[deg]C. It is suggested that limitations to CO2 assimilation are caused by metabolic restrictions that can be differentiated between those occurring in the range of 20 to 30[deg]C and 30 to 35[deg]C. It is likely that changes in the capacity for Calvin cycle regeneration and starch synthesis affect photosynthesis in the range of 20 to 30[deg]C. But following an increase in temperature from 30 to 35[deg]C, the supply of reducing power becomes limiting. From analysis of adenylate concentration, transthylakoid energization, and, indirectly, NADPH/NADP+ ratio, it was concluded that the limitation in the assimilatory power was due to an oxidation of the NADPH/NADP+ pool. In the range of 30 to 35[deg]C, the photosystem I quantum yield increased and photosystem II maintained its value. We conclude that the reorganization of thylakoids observed at 30 to 35[deg]C increased the excitation of photosystem I, inducing an increase in cyclic electron transport and a decrease in the supply of NADPH, limiting carbon assimilation.