["Psychology &Marketing, EarlyView. ", "\nABSTRACT\nEthical consumption is central to responsible marketing strategy, yet consumers routinely fail to act on stated ethical intentions a gap frequently attributed to implicit affective and cognitive processes that self‐report measures cannot adequately capture. This multistudy investigation examines how stable individual differences in personality and empathy shape neurophysiological responses to ethical product stimuli and, in turn, drive real‐world purchasing behavior. Study 1 (N = 96) combined electroencephalography (EEG) and galvanic skin response (GSR) in a controlled laboratory setting, exposing participants to 48 ethical versus conventional product stimuli across 24 matched product categories. Frontal alpha asymmetry (FAA) and GSR amplitude both differentiated stimulus conditions, with conscientiousness, agreeableness, empathic concern, and moral identity emerging as significant neurophysiological moderators. Study 2 (N = 143) extended these findings to a naturalistic grocery retail environment through wearable electrodermal activity (EDA) wristbands and actual purchase receipts, providing ecological validity. Hierarchical regression revealed that personality traits and mean skin conductance level jointly predicted ethical purchase proportion, with empathic concern amplifying the arousal–purchasing link net of shopping‐context controls (shopping mission, expenditure, basket size, and category composition). Across both studies, individual differences consistently shaped the intensity and directionality of psychophysiological engagement with ethical consumption cues.\n"]