Mental toughness can be conceptualised as a set of attributes that allow people to deal effectively with challenges, stressors and pressure. Recent work has suggested that it may be a valuable construct to consider within educational settings. The current studies explored the associations between mental toughness and educational transitions. Study 1 examined the relationships between mental toughness and concerns about moving to a new school in 105 children aged 12–13 years of age. The results revealed significant relationships between several aspects of mental toughness, but particularly confidence in abilities, and children’s concerns. Study 2 examined the relationships between mental toughness and adjustment to university in 200 undergraduate students at various stages of their course. The results revealed a role for several aspects of mental toughness; commitment, control of life, control of emotion, confidence in abilities and interpersonal confidence. The results are discussed in terms of implications for educational practice. It is suggested that measures of mental toughness could be used to identify individuals who may benefit from additional support during transition to a new school or to university, and that future research should explore the potential benefits of mental toughness training.