Radical-mediated transformations have emerged as powerful methods for the synthesis of rare and unnatural branched, deoxygenated, and isomeric sugars. Here, we describe a radical-mediated axial-to-equatorial alcohol epimerization method to transform abundant glycans into rare isomers. The method delivers highly predictable and selective reaction outcomes that are complementary to other sugar isomerization methods. The synthetic utility of isomer interconversion is showcased through expedient glycan synthesis, including one-step glycodiversification. Mechanistic studies reveal that both site- and diastereoselectivities are achieved by highly selective H atom abstraction of equatorially disposed α-hydroxy C-H bonds.