Existing research suggests that temperamental traits that emerge early in childhood may have utility for early detection and intervention for common mental disorders. The present study examined the unique relationships between the temperament characteristics of reactivity, approach-sociability, and persistence in early childhood and subsequent symptom trajectories of psychopathology (depression, anxiety, conduct disorder, and attention-deficit hyperactivity disorder; ADHD) from childhood to early adolescence. Data were from the first five waves of the older cohort from the Longitudinal Study of Australian Children (n = 4983; 51.2% male), which spanned ages 4–5 to 12–13. Multivariate ordinal and logistic regressions examined whether parent-reported child temperament characteristics at age 4–5 predicted the study child’s subsequent symptom trajectories for each domain of psychopathology (derived using latent class growth analyses), after controlling for other presenting symptoms. Temperament characteristics differentially predicted the symptom trajectories for depression, anxiety, conduct disorder, and ADHD: Higher levels of reactivity uniquely predicted higher symptom trajectories for all 4 domains; higher levels of approach-sociability predicted higher trajectories of conduct disorder and ADHD, but lower trajectories of anxiety; and higher levels of persistence were related to lower trajectories of conduct disorder and ADHD. These findings suggest that temperament is an early identifiable risk factor for the development of psychopathology, and that identification and timely interventions for children with highly reactive temperaments in particular could prevent later mental health problems.