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Envy is a typical negative social emotion that has negative effects on the physical and mental health of individuals. In this study we examined the relationship between the Big Five personality traits and envy, and the mediating role of emotional intelligence in these associations. Participants were 811 university students in China who completed the Revised NEO Personality Inventory, the Wong and Law Emotional Intelligence Scale, and the Dispositional Envy Scale. Mediation analysis results showed that emotional intelligence played a partial mediating role in the relationships between neuroticism and envy and between extraversion and envy, and played a complete mediating role in the relationships between agreeableness and envy, between openness and envy, and between conscientiousness and envy. We have found evidence for the personality basis of envy and provided insight into the underlying mechanisms between personality and envy.