This study examined the relationships between Big Six personality and entrepreneurial intention, inclusive of the mediating role of entrepreneurial self-efficacy in the Chinese context. Survey data from 280 college students reveal that Emotional Stability, Conscientiousness, Extraversion, and Interpersonal Relationship were positively associated with entrepreneurial intention. Agreeableness and Openness, however, had no effect on entrepreneurial intention in this study. Mediation analysis further indicated that Emotional Stability, Conscientiousness, Extraversion, and Interpersonal Relationship affected entrepreneurial self-efficacy, thus playing an indirect impact on entrepreneurial intention. In contrast, Agreeableness and Openness had no mediating role in the present study. These findings validate the bridge mechanism of entrepreneurial self-efficacy underlying the relationships between Big Six personality and entrepreneurial intention. These results highlight the direct role of sustainable personality as a predictor of entrepreneurial intention, especially as we note the decisive effect of the Interpersonal Relationship dimension in the Chinese context for the first time.