AbstractSingle‐phase Na1.2V3O8 materials with single and hierarchical nanobelt morphologies were prepared by using a versatile electrospinning technique by altering the sintering profiles. On the basis of characterization by field‐emission scanning electron microscopy and high‐resolution transmission electron microscopy, the formation mechanisms of products with tunable morphologies are discussed. The products obtained are employed as cathode materials for lithium‐ion batteries. Their electrochemical activities are demonstrated through galvanostatic cycling and cyclic voltammetry. The non‐agglomerated, single nanobelts with exposed (100) facets, which serve as channels for facile lithium diffusion, are capable of exhibiting higher maximum capacities of approximately 218 mAh g−1 compared to hierarchical nanobelts with a maximum capacity of approximately 197 mAh g−1 versus Li/Li+ at a current density of 200 mA g−1. Their associated reversible capacities are approximately 207 and 173 mAh g−1, respectively, after 100 cycles. Single nanobelts with individual belt‐like structures and preferred facet orientation also exhibit better rate capabilities.