Basic requirements for advanced and practical supercapacitors need electrode materials with strong stability, high surface area, well-defined porosity, and enhanced capability of ion insertion and electron transfer. It is worth mentioning that the two-dimensional cluster-based Ni/Co−organic layer (Ni 0.7 Co 0.3 -CMOL) inherits high stability from the Kagoḿe lattice and shows excellent pseudocapacitance behavior. As an optimized atomic composition, this crystalline CMOL exhibits excellent performance and stability both in 1.0 M KOH and All-Solid-State Flexible Asymmetric Supercapacitor (ASCs). The specific capacitance values are 1211 and 394 F g −1 and the energy density is 54.67 Wh kg −1 at 1 A g −1 . Good cycling stability is characterized by its capacitance retention, maintained at 92.4% after 5000 cycles in a three-electrode system and 90% after 2000 cycles at 20 A g −1 for assembled All-Solid-State Flexible ASCs. An in situ XRD technique was used in the three-electrode system, which showed that there was no signal of crystalline substance that affected the cyclic stability of the material while charging and discharging. These superior results prove that Ni 0.7 Co 0.3 -CMOL is a promising candidate for supercapacitor applications.