The extensive and increasing use of structural neuroimaging in the neurosciences rests on the assumption of an intimate relationship between structure and function in the human brain. However, few studies have examined the relationship between advanced magnetic resonance imaging (MRI) indices of cerebral structure and conventional measures of cerebral functioning in humans. Here we examined whether MRI-based morphometric measures of early visual cortex-estimated using a probabilistic anatomical mask of primary visual cortex (V1)-can predict the amplitude of the visual evoked potential (VEP), i.e., an electroencephalogram signal that primarily reflects postsynaptic potentials in early visual cortical areas. We found that left, right, and total V1 surface area positively predicted the VEP amplitude. In addition, we showed, using whole brain analysis of local surface areal expansion/contraction, that the association between VEP amplitude and surface area was highly specific for regions within bilateral V1. Together, these findings indicate a strong, selective relationship between MRI-based structural measures and functional properties of the human cerebral cortex.