Metal‐organic frameworks (MOFs) have been widely concerned as functional materials with excellent properties. However, most MOFs are of poor electrical conductivity, which hinders their further application in electrochemical fields. Fortunately, the emergence of intrinsically conductive MOFs (c‐MOFs) alleviates this problem. Layered double hydroxides (LDHs) possess Faraday redox reactivity, which is favorable to capacitors. In this paper, we combined c‐MOFs with LDHs and prepared a series of NiCo‐LDH@M‐HHTP(‐EtOH) (M = Ni or Co; HHTP = 2,3,6,7,10,11‐hexahydroxytriphenylene) multilayer nanoarrays, and the effects of solvent on the morphology and energy storage properties of the materials were investigated. When NiCo‐LDH@Co‐HHTP‐EtOH is applied as an electrode material in supercapacitors, it exhibits a capacitance of 830 F g‐1 at 1 A g‐1. What’s more, it exhibits high energy density and excellent rate performance when assembled in aqueous asymmetric supercapacitors.