In this study, a facile and inexpensive and self-assembled strategy to massively fabricate Ni/Co layered double hydroxides (LDHs) is developed under mild reaction conditions (55 °C). The resulting composite material displays a special three-dimensional hierarchical microsphere structure with well-defined flower-like configuration. The fabrication mechanism can be ascribed to stepwise and regular reaction process of nanoparticles and nanosheets gradually growing to nanopetals and then assembling into flower-like microspheres, based on the systematically investigation of various reaction factors including the Ni:Co feeding ratio, the reaction time and the initial pH-value. Because of its large surface, ultrathin feature and synergetic results of this Ni/Co LDHs nanosheets (20 nm), these Ni/Co-LDHs microspheres deliver an excellent capacitance value about 2228 F·g–1 (1 A·g–1). An all-solid-state flexible asymmetric supercapacitor is designed and assembled by exploiting this Ni/Co-LDHs as the positive materials, which exhibits energy density of 165.51 Wh·kg1– at 1.53 KW·kg1–. It may have vast potential significance in personal wearable equipment. Moreover, this monolithic design provides a promising approach for large scale fabrication of other LDHs materials.