Understanding the network structure of white matter communication pathways is essential for unraveling the mysteries of the brain's function, organization, and evolution. To this end, we derive a unique network incorporating 410 anatomical tracing studies of the macaque brain from the Collation of Connectivity data on the Macaque brain (CoCoMac) neuroinformatic database. Our network consists of 383 hierarchically organized regions spanning cortex, thalamus, and basal ganglia; models the presence of 6,602 directed long-distance connections; is three times larger than any previously derived brain network; and contains subnetworks corresponding to classic corticocortical, corticosubcortical, and subcortico-subcortical fiber systems. We found that the empirical degree distribution of the network is consistent with the hypothesis of the maximum entropy exponential distribution and discovered two remarkable bridges between the brain's structure and function via network-theoretical analysis. First, prefrontal cortex contains a disproportionate share of topologically central regions. Second, there exists a tightly integrated core circuit, spanning parts of premotor cortex, prefrontal cortex, temporal lobe, parietal lobe, thalamus, basal ganglia, cingulate cortex, insula, and visual cortex, that includes much of the task-positive and task-negative networks and might play a special role in higher cognition and consciousness.