With high conductivity, high melting point and large specific capacity, molybdenum dioxide (MoO2) nanorods have a wide application prospect in the field of electrode materials for supercapacitors. Although there are many methods to prepare MoO2 nanorods, most of them have disadvantages of a complicated process, low yield, high production cost and easy to introduce impurities. Moreover, the prepared MoO2 products have the characteristics of non-uniform morphology, poor dispersibility and inferior electrochemical performances. In this work, the precursor of peroxymolybdic acid prepared by hydrogen peroxide and molybdenum powder was used as the source of molybdenum, and PEG (8000) was used as the template. The molybdenum-containing hybrid with a band structure was prepared by mixing the precursor and template with stirring and thermal insulation. The nano-rod-shaped MoO2 was prepared through a two-stage hydrometallurgical process using the hybrid compound as raw material. X-ray diffractometer (XRD), X-ray photoelectron spectrometer (XPS), X-ray energy spectrometer (EDS) and scanning electron microscope (SEM) were used to analyze the phase, surface composition and morphology of the obtained MoO2 nanorods. The electrochemical capacitance behavior of MoO2 nanorods was studied using a three-electrode system and two-electrode system, and the performance of MoO2 nanorods as electrode assembly capacitors was also investigated. The results showed that the prepared MoO2 had a rod-like structure with 500 to 800 nm in length and with 100 to 200 nm in width. The MoO2 had uniform morphology and size with good dispersion and high purity. The specific capacitance of MoO2 nanorods was 366.7 F/g for the three-electrode system at the current density of 1 A/g, and the specific capacitance for the two-electrode system was 290.4 F/g, and the capacitance retention rate was higher than 72% after 2000 cycles of charging and discharging at 5 A/g current density, both showing the good electrochemical performance of MoO2 nanorods. The research results of this study can provide a new method for the preparation of other nano metal oxides.