Mental toughness has frequently been associated with successful performance in sport; however, recent research suggests that it may also be related to academic performance in Higher Education. In a series of three exploratory studies, we examined the relationship between mental toughness and different aspects of educational performance in adolescents aged 11–16, focusing on academic attainment, school attendance, classroom behaviour and peer relationships. Study 1 revealed significant associations between several aspects of mental toughness (but particularly control of life) and academic attainment and attendance. Study 2 revealed significant associations between several aspects of mental toughness (but again particularly control of life) and counterproductive classroom behaviour. Finally, Study 3 demonstrated significant associations between aspects of mental toughness (confidence in abilities and interpersonal confidence) and peer relationships. The results are discussed in terms of the potential value of mental toughness as a useful concept in education.