Electrode materials with a three-dimensional (3D) layered framework and excellent electrochemical stability can provide a new avenue for enhancing the overall performance of promising sodium ion batteries. Here, we show that layered monoclinic (m) - ZnV2O6 nanobelts with high chemical activity for Na-ion energy storage have been effectively fabricated via a rapid microwave irradiation method over the reaction time of 8h, in which the fabricating efficiency is 24.5 times greater in comparison with the traditional hydrothermal method. The morphology and phase evolutions were verified by means of X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. This study also proposes the “topotactic transformation−Ostwald ripening” mechanism in layered m-ZnV2O6 nanobelts, from one-dimensional (1D) m-Zn2V2O7 with tunnel structure to a 3D m-ZnV2O6 layered structure. In particular, the m-ZnV2O6 nanobelt anode exhibited a high discharge capacity of 480.5mAhg−1 at a current density of 10mAg−1, and maintained the considerable discharge capacity of 246.9mAhg−1 at the 100th cycle. The very preliminary results are promising and confirming that layered metallic vanadium can give a new insight into designing novel anode materials for high-efficiency energy storage in sodium ion batteries.