Prolonged drought stress combined with high leaf temperatures can induce programmed leaf senescence involving lipid peroxidation, and the loss of net carbon assimilation during early stages of tree mortality. Periodic droughts are known to induce widespread tree mortality in the Amazon rainforest, but little is known about the role of lipid peroxidation during drought-induced leaf senescence. In this study, we present observations of green leaf volatile (GLV) emissions during membrane peroxidation processes associated with the combined effects of high leaf temperatures and drought-induced leaf senescence from individual detached leaves and a rainforest ecosystem in the central Amazon. Temperature-dependent leaf emissions of volatile terpenoids were observed during the morning, and together with transpiration and net photosynthesis, showed a post-midday depression. This post-midday depression was associated with a stimulation of C5 and C6 GLV emissions, which continued to increase throughout the late afternoon in a temperature-independent fashion. During the 2010 drought in the Amazon Basin, which resulted in widespread tree mortality, green leaf volatile emissions (C6 GLVs) were observed to build up within the forest canopy atmosphere, likely associated with high leaf temperatures and enhanced drought-induced leaf senescence processes. The results suggest that observations of GLVs in the tropical boundary layer could be used as a chemical sensor of reduced ecosystem productivity associated with drought stress.