Given that combined merits of both compositions and novel structures play important roles in energy storage of electrode materials, we herein use [CH3NH3][NixCo1-x(HCOO)(3)] as self-sacrificed precursors to synthesize structure-controlled hollow nickel cobalt phosphides microcubes. The as-obtained hollow NiCoP-2 displays the highest specific capacity of 629 C g(-1) at 1 A g(-1) and superior cycling stability with 81.3% capacitance retention at 6 A g(-1) after 8000 cycles. Moreover, the asymmetric supercapacitor composed of NiCoP-2 and commercial active carbon (YP-80F) presents the remarkable battery storage performance in terms of outstanding specific capacitance (121.5 F g(-1) at 1 A g(-1)), excellent cycling durability (90.1% capacitance retention after 10,000 cycles) and high energy density of 43.2 Wh kg(-1) at a power density of 801.6 W kg(-1). The attractive performance can be ascribed to superiority of the transition metal phosphides, hollow structures, as well as synergism between Ni and Co. (C) 2019 Elsevier Inc. All rights reserved.