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While behavioral and policy interventions such as ecolabels (e.g., the Energy Star label) promote sustainable purchases, the reason for their influence remains unclear. We combined incentive-compatible purchasing experiments, neuroimaging assessments, and a national stated choice survey to examine how the Energy Star label might influence choices of light bulbs within individuals, across individuals (n = 36), and out-of-sample in a national survey (n = 1550). Presence of the Energy Star label increased activity in neural regions associated with positive affective responses that predicted purchasing (e.g., the Nucleus Accumbens or NAcc), particularly in more impulsive individuals. Group-averaged NAcc activity could also account for consumer demand for similar sustainable product combinations in a national survey. These findings suggest that ecolabels may leverage affective responses in individuals as well as markets to promote sustainable purchases, which might inform the promotion of sustainable products.