The article reports the synthesis and characterization of hierarchical MnMoO4/CoMoO4 heterostructured nanowires, which exhibit enhanced supercapacitor performance. The nanowires were prepared using a simple refluxing method under mild conditions, with the MnMoO4 nanowires serving as the backbone material and the CoMoO4 shell thickness tunable by adjusting the molar ratio of Mn and Co sources. The heterostructures were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and Raman spectroscopy. The electrochemical properties of the hierarchical MnMoO4/CoMoO4 nanowires were evaluated in a three-electrode system in 2 M NaOH solution, showing a specific capacitance of 187.1 F g−1 at a current density of 1 A g−1 and good reversibility with a cycling efficiency of 98% after 1,000 cycles. The crystal growth mechanism was explained through 'self-assembly' and 'oriented attachment' processes, which contributed to the improved electrochemical performance. The hierarchical structure and enhanced surface area of the nanowires were identified as key factors in their superior performance.The article reports the synthesis and characterization of hierarchical MnMoO4/CoMoO4 heterostructured nanowires, which exhibit enhanced supercapacitor performance. The nanowires were prepared using a simple refluxing method under mild conditions, with the MnMoO4 nanowires serving as the backbone material and the CoMoO4 shell thickness tunable by adjusting the molar ratio of Mn and Co sources. The heterostructures were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and Raman spectroscopy. The electrochemical properties of the hierarchical MnMoO4/CoMoO4 nanowires were evaluated in a three-electrode system in 2 M NaOH solution, showing a specific capacitance of 187.1 F g−1 at a current density of 1 A g−1 and good reversibility with a cycling efficiency of 98% after 1,000 cycles. The crystal growth mechanism was explained through 'self-assembly' and 'oriented attachment' processes, which contributed to the improved electrochemical performance. The hierarchical structure and enhanced surface area of the nanowires were identified as key factors in their superior performance.