Little is known about the effects of environmental enrichment on psychophysiological measures of arousal and orienting in humans. This study tests the hypothesis that early educational and health enrichment is associated with long-term increases in psychophysiological orienting and arousal. One hundred children were experimentally assigned to a two-year enriched nursery school intervention at ages 3–5 years and matched at age 3 years on psychophysiological measures, gender, and ethnicity to 100 comparisons who received the normal educational experience. Children were retested 6–8 years later at age 11 years on skin conductance (SC) and electroencephalogram (EEG) measures of arousal and attention during pre- and postexperimental rest periods and during the continuous performance task. Nursery enrichment was associated with increased SC amplitudes, faster SC rise times, faster SC recovery times, and less slow-wave EEG during both rest and CPT conditions. This is believed to be the first study to show that early environmental enrichment is associated with long-term increases in psychophysiological orienting and arousal in humans. Results draw attention to the important influence of the early environment in shaping later psychophysiological functioning.