Measuring consumers’ emotion with self-report methods has remained a challenge in luxury marketing. In comparison to self-report measure, psychophysiological methods promise to provide a scientific, objective and sensitive measure of the neurophysiological basis of emotional processes. The objective of this paper is to: (1) examine the feasibility of using psychophysiological methods in luxury marketing; (2) compare the capability of psychophysiological methods to capture emotion beyond those measured by self-report methods; and (3) better under luxury consumers’ emotion processes. In this study, brain wave analysis, heart rate, skin conductance, and facial expression were used to investigate consumers’ emotional response toward luxury marketing stimuli. The psychophysiological findings identified anger, interest and arousal as key emotional processes that affect consumers’ reaction to luxury branding. These findings show that psychophysiological methods are not only feasible in informing luxury branding practices but also provide insights into luxury consumers’ emotional experience beyond those captured by self-report methods.