The effect of a single oral dose of caffeine was examined in a randomised double-blind placebo-controlled repeated-measures cross-over study. Eighteen children with AD/HD, aged between 8 and 13 years, were individually age- and gender-matched with a control group. All children participated in two sessions, one week apart. Skin conductance level (SCL) from a 3 min eyes-closed epoch, commencing 30 min after ingestion of caffeine or placebo, was examined. Across conditions, mean SCL was lower in the AD/HD group than controls, confirming hypoarousal in AD/HD. Caffeine produced an increase in SCL, and this increase did not differ between the groups. However, arousal increases were dose-dependent in controls, but not in AD/HD. Rather, caffeine-induced arousal increases in the AD/HD group were positively related to their hyperactivity/impulsivity levels. This suggests an anomalous arousal mechanism in AD/HD functionally related to impairment in one symptom dimension.