The fabrication of an ideal electrode architecture consisting of robust three dimensional (3D) nanowire networks have gained special interest for energy storage applications owing to the integrated advantages of nanostructures and microstructures. In this work, 3D MoO2 nanotextiles assembled from highly interconnected elongated nanowires are successfully prepared by a facile stirring assisted hydrothermal method and followed by an annealing process. In addition, a methylbenzene/water biphasic reaction system is involved in the hydrothermal process. When used as an anode material in Li ion batteries (LIBs), this robust MoO2 nanotextiles exhibit a high reversible capacity (860.4 mAh g−1 at 300 mA g−1), excellent cycling performance (89% capacity retention after 160 cycles) and rate capability (577 mAh g−1 at 2000 mA g−1). Various synthetic factors to the fabrication of 3D nanotextiles structure are discussed here and this design of 3D network structures may be extended to the preparation of other functional nanomaterials.