<p>Metal–organic frameworks are regarded as promising candidates for advanced supercapacitor applications because of their extremely large surface areas and highly porous architectures. However, their practical use is often limited by sluggish charge transport and insufficient stability under alkaline conditions. In this work, a simple dissolution–reconstruction approach is introduced to fabricate a sandwich-structured GO@Ni-MOF@NiAl-LDHs composite, effectively overcoming these limitations. In this system, NiAl layered double hydroxides act as reservoirs that capture and reorganize nickel ions released from the Ni-MOF during processing. The incorporation of GO enhances electrical conductivity and exposes additional electrochemically active sites. Furthermore, the layered sandwich configuration facilitates faster electron transport and lowers electrolyte diffusion resistance, thereby improving overall electrochemical performance. At the same time, the layered, sandwich-like configuration shortens electron-migration lengths and decreases ion-diffusion resistance. As a result, the electrode exhibits markedly enhanced electrochemical behavior, which originates from the improved intrinsic activity following the structural evolution from GO@Ni-MOF@AlOOH to GO@Ni-MOF@NiAl-LDHs during cycling. The optimized material achieves a high specific capacitance of 2382 F·g⁻¹ at 1 A g⁻¹ in a three-electrode system. When paired with GO, the GO@Ni-MOF@NiAl-LDHs based device reaches an energy density of 494 Wh kg⁻¹; at 654 W kg⁻¹. Overall, this dissolution-reconstruction strategy opens a promising avenue for developing advanced materials for energy-storage technologies.</p><p></p>