In this work, carbon-free, porous, and micro/nanostructural Zn2GeO4 nanofibers (p-ZGONFs) have been prepared via a dissolution-recrystallization-assisted electrospinning technology. The successful electrospinning to fabricate the uniform p-ZGONFs mainly benefits from the preparation of completely dissolved solution, which avoids the sedimentation of common Ge-containing solid-state precursors. Electrochemical tests demonstrate that the as-prepared p-ZGONFs exhibit superior Li-storage properties in terms of high initial reversible capacity of 1075.6 mA h g(-1), outstanding cycling stability (no capacity decay after 130 cycles at 0.2 A g(-1)), and excellent high-rate capabilities (e.g., still delivering a capacity of 384.7 mA h g(-1) at a very high current density of 10 A g(-1)) when used as anode materials for lithium ion batteries (LIBs). All these Li-storage properties are much better than those of Zn2GeO4 nanorods prepared by a hydrothermal process. The much enhanced Li-storage properties should be attributed to its distinctive structural characteristics including the carbon-free composition, plentiful pores, and macro/nanostructures. Carbon-free composition promises its high theoretical Li-storage capacity, and plentiful pores cannot only accommodate the volumetric variations during the successive lithiation/delithiation but can also serve as the electrolyte reservoirs to facilitate Li interaction with electrode materials.