Layered double hydroxides (LDHs) exhibit excellent electrochemical performance in alkali solutions. However, their low conductivity and poor cycle stability limit their application. In this work, Ni-Mn LDH was grown on activated carbon nanofibers (ACNFs) and then phosphidated to obtain an electrode material with a three-dimensional core–shell structure ([email protected]). This composite combines the electrochemical activity of the two-dimensional phosphidated nanosheets with the structural stability of the one-dimensional nanofibers. The resulting [email protected] electrode exhibits a high specific capacitance of 1077 F g−1 at 1 A g−1, which is 4.9 times higher than that of a non-phosphidated [email protected] LDH electrode, and retains stability of 88.53% at a high current density of 10 A g−1 even after 5000 cycles. Moreover, an asymmetrical supercapacitor featuring an [email protected] positive electrode achieves comparatively prominent specific energy of 56.25 Wh kg−1 at 806.13 W kg−1, respectively. Therefore, [email protected] as electrode material has great potential for application in supercapacitors.