To explore the relationship between brand awareness and purchase intention of new energy vehicles (NEV) and their mechanism, 560 users with recent purchase intention of NEV were surveyed by using the brand awareness scale, perceived value scale, purchase intention scale, and green consumption value scale. The results show that: (1) under the condition of controlling for gender and age, brand awareness can significantly and positively predict the purchase intention of NEV users, (2) brand awareness predicts the purchase intention of NEV users through the mediation of perceived value, and (3) the relationship between brand awareness and the purchase intention is moderated by the green consumption value. Specifically, individuals with a higher level of green consumption values exhibit a stronger correlation between brand awareness and purchase intention compared to those with lower levels of consumption values. The findings of this study shed light on the mechanisms underlying the purchase intention of NEV brand users and offer valuable enlightenments for the marketing strategies of NEV brands.