Diffusion-weighted imaging can be used to assess the microscopic properties of measured tissues, providing insights into the architecture of neural tissues and how they change in physiological and pathological states. Such imaging data can be readily quantified to provide numerical values of parameters that have clinical relevance, particularly in regard to cellular constituents of tumours, chemical contents of cysts, the integrity of neuronal cell bodies and myelin sheaths. Diffusion based techniques have proven to be particularly useful in investigating cerebral infarction, cerebral infections, epidermoid and other cysts, cerebral tumours, and white matter disorders. The purpose of this review is to introduce key concepts in diffusion imaging and illustrate how it may be applied to clinical practice, with particular reference to head injury.