Ventral striatal activation measured with functional magnetic resonance imaging (fMRI) and feedback negativity amplitude measured with event-related potentials (ERPs) are each enhanced during reward processing. Recent research has found that these two neural measures of reward processing are also related to one another, such that increases in ventral striatal activity are accompanied by increases in the amplitude of the feedback negativity. Although there is a long history of research implicating the midbrain dopamine system in reward processing, there has been little research into the possibility that structural variability in the midbrain may be linked to functional variability in reward reactivity. Here, we used structural MRI to measure midbrain volumes in addition to fMRI and ERP measures of functional neural reactivity to rewards in a simple gambling task. The results suggest that as midbrain volumes increase, fMRI reward reactivity in the ventral striatum and medial prefrontal cortex also increases. A similar relationship exists between midbrain structure and the amplitude of the feedback negativity; further, this relationship is mediated specifically by activity in the ventral striatum. These data demonstrate convergence between neuroanatomical, hemodynamic, and electrophysiological measures. Thus, structural variability in the midbrain relates to variability in fMRI and ERP measures of functional reward reactivity, which may play a critical role in reward-related psychopathologies and the treatment of these disorders.