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This paper examines the role of trait emotional intelligence (‘trait EI') in academic performance and in deviant behavior at school on a sample of 650 pupils in British secondary education (mean age ≈16.5 years). Trait EI moderated the relationship between cognitive ability and academic performance. In addition, pupils with high trait EI scores were less likely to have had unauthorized absences and less likely to have been excluded from school. Most trait EI effects persisted even after controlling for personality variance. It is concluded that the constellation of emotion-related self-perceived abilities and dispositions that the construct of trait EI encompasses is implicated in academic performance and deviant behavior, with effects that are particularly relevant to vulnerable or disadvantaged adolescents.