Several newer magnetic resonance imaging (MRI) techniques are increasingly being applied to the study of white matter development and pathology across the lifespan. These techniques go beyond traditional macrostructural volumetric methods and provide valuable information about underlying tissue integrity and organization at the microstructural and biochemical levels. We first provide an overview of white matter development and discuss the role of white matter and myelin in cognitive function. We also review available studies of development that have employed traditional volumetric measures. Then, we discuss the contributions of four newer imaging paradigms to our understanding of brain development and aging. These paradigms are Diffusion Tensor Imaging (DTI), Magnetization Transfer Imaging (MTI), T2-Relaxography, and Magnetic Resonance Spectroscopy (MRS). Studies examining brain development during childhood and adulthood as well as studies of the effects of aging are discussed.