Highly crumpled graphene nanosheets (GS) with a BET surface area as high as 722.1 m2 g−1 is prepared by a thermal exfoliation method. A systematical investigation is performed on the electrochemical performances of porous Ni2P/GS nanocomposite synthesized by the low temperature solid state reaction method. It is shown that Ni2P nanoparticles anchor on graphene sheets producing a porous structure and GS have beneficial effects on the electrochemical properties of Ni2P nanoparticles when investigated as pseudocapacitor materials. The novel Ni2P/GS composite electrode exhibits a superior specific capacitance of 1912 F g−1 and 888 F g−1 at current densities of 5 and 50mAcm−2, respectively. The specific capacitance decreases to 1473 F g−1 after 2500 cycles, suggesting its excellent cycling stability. It is confirmed that the GS with good electrical conductivity serve as a conducting network for fast electron transfer between the active materials and charge collector, as well as buffered spaces to accommodate the volume expansion/contraction during cycling, thus, leading to enhancement of the electrochemical properties of the Ni2P electrode.