As a marketing strategy, goods-to-service brand extension has been extensively used for luxury brands. However, little is known about the effectiveness of understanding the neural mechanisms during the evaluation of luxury goods-to-service brand extension. In this study, event-related potentials (ERPs) were applied to investigate the cognitive processes during the evaluation of goods-to-service brand extension in the luxury sector. First, participants were presented with 2 sequential text stimuli of the luxury brand name (S1) in different industries and the extended service name (S2). These stimuli involve 2 conditions, namely, high-fit (HF) groups and low-fit (LF) groups. Then, participants were asked to decide whether or not to accept the given brand extension. Behavioral data show that a higher acceptance rate exists in HF than LF. Neurophysiologically, LF conditions triggered a larger N2 amplitude and N400 amplitude than HF conditions. Moreover, compared with LF conditions, HF conditions evoked a more positive late positive potential (LPP) amplitude. These results may reflect differences in perceived conflict, semantic categorization, and arousal between LF and HF conditions. These results provide evidence for the brain’s three-stage evaluation process of goods-to-service brand extension and provide neurological evidence for marketing researchers in evaluating preformed luxury brand extension strategy.