In this work, Ni2P/NiS2 composite hollow sphere is synthesized for supercapacitor applications. Benefiting from the phase boundaries between the Ni2P and NiS2 and the resultant synergistic effect, Ni2P/NiS2 composite exhibits rapid electron and ion transport rate and superior electrochemical property over the pristine electrode materials. The Ni2P/NiS2 composite demonstrates a maximum gravimetric capacity of 212.7 mAh g(-1) at the current density of 2 A g(-1) and a stable cycling performance. This work presents an effective route to enhance the electrochemical property by preparing the composite with phase boundaries. (C) 2017 The Electrochemical Society. All rights reserved.