The neural mechanisms that mediate metacognitive ability (the capacity to accurately reflect on one's own cognition and experience) remain poorly understood. An important question is whether metacognitive capacity is a domain-general skill supported by a core neuroanatomical substrate or whether regionally specific neural structures underlie accurate reflection in different cognitive domains. Providing preliminary support for the latter possibility, recent findings have shown that individual differences in metacognitive ability in the domains of memory and perception are related to variation in distinct gray matter volume and resting-state functional connectivity. The current investigation sought to build on these findings by evaluating how metacognitive ability in these domains is related to variation in white matter microstructure. We quantified metacognitive ability across memory and perception domains and used diffusion spectrum imaging to examine the relation between high-resolution measurements of white matter microstructure and individual differences in metacognitive accuracy in each domain. We found that metacognitive accuracy for perceptual decisions and memory were uncorrelated across individuals and that metacognitive accuracy in each domain was related to variation in white matter microstructure in distinct brain areas. Metacognitive accuracy for perceptual decisions was associated with increased diffusion anisotropy in white matter underlying the ACC, whereas metacognitive accuracy for memory retrieval was associated with increased diffusion anisotropy in the white matter extending into the inferior parietal lobule. Together, these results extend previous findings linking metacognitive ability in the domains of perception and memory to variation in distinct brain structures and connections.