Sigma power during sleep is associated with cognitive abilities in healthy humans. We examined the relationship between sigma power in sleep EEG and intelligence and alertness in schoolchildren with ADHD (n = 17) in comparison to mentally healthy children (n = 16) and adults (n = 23). We observed a positive correlation between sigma power in sleep stage 2 and IQ in healthy adults but a negative correlation in children with ADHD. Furthermore, children with ADHD showed slower reaction times in alertness testing than both control groups. In contrast, only healthy children displayed a positive correlation between sigma power and reaction times. These data suggest that the associations between sigma power and cognitive performance underlie distinct developmental processes. A negative association between IQ and sigma power indicates a disturbed function of sleep in cognitive functions in ADHD, whereas the function of sleep appears to be matured early in case of motor-related alertness performance.