Background: Dehydroepiandrosterone (DHEA) is an adrenal androgen which is stress responsive and a trigger for pubertal maturation. Studies on basal DHEA suggest protective benefits against anxiety and depression, yet it is unknown whether DHEA responsivity is protective. Methods: Structural equation modeling examined salivary DHEA responses to a public speaking task (PST) and parent-child conflict discussion paradigm (CDP) in adolescents. Results and conclusions: DHEA levels were higher in girls than boys, and in older and more physically developed adolescents, indicative of DHEA's function during pubertal maturation. DHEA levels increased during the PST, indicating responsiveness of DHEA to acute stressors. Across both tasks, girls with internalizing problems showed sharper rises in DHEA by 40 minutes post-task, ending with the highest DHEA. In internalizing adolescent girls, DHEA may serve as a marker of responsivity in stressful or conflictual contexts. A failure of these girls with internalizing problems to show a normal diurnal decline in the afternoon extended this conclusion to naturalistic environments. DHEA may be one possible mechanism linking stress responsivity and physical maturation that helps to explain adolescents' risk for psychopathology within a biobehavioral framework.