This review provides an overview of brain structural imaging methods for examining neural correlates of performance, skill and learning in the domain of language and beyond. We first provide a historical overview of structural imaging, followed by an overview of brain structural measures/variables, assumptions regarding their neurophysiological basis, a description of the challenges and solutions for using structural imaging for studying receptive speech, a review of key empirical contributions in the field, and finally, some future directions for this research approach. Studies having examined multiple structural measures and modalities in parallel are still sparse. However, recent methodological advances which allow the non-invasive estimation of regional distribution of histological properties such as myelination, along with the increasing resolution of in vivo structural imaging are opening new and exciting avenues which will enable a better understanding of the brain structural underpinnings of language, and of the physiological relevance of these structural features.