In neural systems, form and function are intimately linked; the communication dynamics across networked areas depends on the organization and integrity of the connections between them (i.e., axons and tracts). With the growth of diffusion-weighted imaging (DWI) and fiber tractography tools over the past decade, it has become possible to visualize the physical architecture of the human brain at an unprecedented resolution. This information has provided the first glimpses into the component circuitry supporting cognition, presenting a unique opportunity for cognitive neuroscientists. For the first time we can visualize the connections in the living brain, allowing us to measure individual differences in anatomical connectivity, relate this connectivity to brain function, and gain insights into the link between white matter architecture and behavior. In many ways, this technology is still in its infancy and its full potential has not yet been realized. Here, I outline the importance of understanding neuroanatomical connectivity as a hard constraint on neural computation. Beginning with an overview of the typical patterns of connectivity seen in neural systems, I go on to show how current neuroimaging tools can visualize several different types of connectivity in the brain. By highlighting recent findings showing how neuroanatomical organization and brain function are related during cognitive tasks, I emphasize the utility that structural brain mapping approaches can have for the broader social and behavioral sciences.