Efficient attention is pivotal for cognitive functioning, and individual differences in attentional functions are likely related to variations in structural properties of the brain. Attention is supported by separate processes, and models of the relationship between attention and brain structure must take this into account. The Attention Network Test (ANT) yields behavioral measures of 3 independent attentional components: executive control (EC), alerting, and orienting. EC relates to resolving cognitive interference, alerting refers to continuous maintenance of a vigilant state, and orienting to selection of and orienting toward sensory information. Evidence from functional neuroimaging studies suggests that the ANT components recruit different cortical networks. However, the structural correlates are not established. Therefore, ANT scores were correlated with cortical thickness across the brain surface in 268 healthy adults spanning 20-84 years of age. Specific correlations were found between cortical thickness and EC and alerting in regions implicated by functional neuroimaging and lesion studies, including anterior cingulate, lateral prefrontal, and right inferior frontal gyri for EC and parietal areas for alerting. The brain-behavior correlations were relatively stable across adulthood, indicating that factors influencing cortical maturation rather than aging-related atrophy specifically were instrumental in shaping the structural foundation for visuospatial attention in adults.