Silver molybdate (Ag₆Mo₁₀O₃₃) exhibits excellent catalytic properties and photocatalytic degradation owing to its unique chemical and structural characteristics, but its prospective applications in electrochemistry energy storage have not received sufficient attention. Herein, the Ag₆Mo₁₀O₃₃ meso/nanowires with superior morphological characteristics are fabricated employing a high-efficient microwave irradiation method. Furthermore, the novel synthesizing mechanism of ultralong Ag₆Mo₁₀O₃₃ mesowires is also proved to be a “self-assembly-dissolution-recrystallization-Ostwald-ripening” process, by exploring through the parallel experiments on the dramatic alterations in topology and size of Ag₆Mo₁₀O₃₃ at continuous reaction time. Additionally, the properties of the ultralong uniform Ag₆Mo₁₀O₃₃ mesowires for the sodium storage are investigated via cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge–discharge. Notably, these as-obtained Ag₆Mo₁₀O₃₃ mesowires exhibit an outstanding initial capacity (1587.9 mAh·g⁻¹), a remarkable specific capacity for the second cycle (817.9 mAh·g⁻¹), and an excellent reversible capacity (551.5 mAh·g⁻¹ after 30 cycles). The superior electrochemical properties of the nanoscaled silver molybdate are ascribed to the lower charge transfer resistance due to the microstructure of the smallest size Ag₆Mo₁₀O₃₃ nanosheets that exhibit a thickness of around 5 nm, which can provide a great contact with the electrolyte, facilitating the rapid diffusion of sodium ions at the electrode/electrolyte interface and the rapid transport of sodium ions within the electrode materials. Thus, the proposed synthetic strategy and achieved deep insights will stimulate the development of Ag₆Mo₁₀O₃₃ for high-safety and long-life sodium ion batteries.