The development of hierarchical core−shell structures and multicomponent metal boride/metal oxide-based composites presents a promising strategy to enhance supercapacitor (SC) performance. In this study, we synthesized a Ni3B@Ni(BO2)2 (0D@2D) core−shell structure and integrated it with V2MoO8 (VMO) rods (1D) to form a Ni3B@Ni(BO2)2/VMO (NB@NBO/ VMO (0D@2D/1D)) composite. This composite was then used as an electrode material on a flexible carbon cloth (CC) substrate for SC applications. The 1D-VMO rods were derived from V-doped MoSe2 nanosheets via hydrothermal synthesis and calcination, while the NB@NBO/VMO composite was obtained by using a liquid-phase method. Structural, compositional, and morphological characterizations were conducted using XRD, XPS, FE-SEM, and TEM-EDS. In a three-electrode system, the NB@NBO/VMO-50 composite showed an impressive Cs of 698 F g−1 at 1 A g−1 , ascribed to its unique core−shell architecture, which enhances contact and faradaic properties, shortens ion diffusion paths, and provides abundant active sites. Notably, the NB@NBO/VMO-50 displayed excellent cyclic stability, retaining 75.1% of its capacitance after 10,000 cycles at 10 A g−1 . This performance is better than those of other electrodes, including pristine VMO/CC, NB/CC, NB@NBO/VMO-25, and NB@NBO/VMO-75. When evaluated in a two-electrode asymmetric SC system, the NB@ NBO/VMO-50/CC||rGO device operated at 1.6 V and delivered a high energy density (ED) of 40.5 Wh kg−1 at a power density (PD) of 800 W kg−1 . It also reached a PD of 16,000 W kg−1 while maintaining an ED of 23.5 Wh kg−1 . The device also showed remarkable long-term durability, maintaining 79.3% of its capacitance and 99.9% Coulombic efficiency after 8000 charge−discharge cycles at 8 A g−1 , demonstrating its strong potential for next-generation energy storage applications.