A facile and template-free one-pot strategy is applied to synthesize MoO2 nanostructured particles via a hydrothermal methodology. Characterizations include X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Brunauer–Emmett–Teller surface area, X-ray photoelectron spectroscopy, Raman scattering spectroscopy, cyclic voltammetry and galvanostatic cycling. The as-annealed MoO2 nanostructured particles exhibit interconnecting and carbon-free features. Due to the unique nanostructure, the MoO2 electrode has a high specific capacity of 824mAhg−1 at C/10 and high reversible capacity of 760mAhg−1 after 30 cycles as anode for lithium storage performance. The interconnected MoO2 nanostructured particles also exhibit an excellent rate performance. Microstructure investigations of the MoO2-based electrode after full-lithiation are performed to elucidate the lithium ion uptake/removal mechanism, which can help us understand the unique cycling behavior of MoO2 material.