Co-Mo-O (Co1.2MoO4.2 center dot 1.3H(2)O)/Ni3S2 nanosheet arrays were in-situ grown directly on Ni foam (NF) by a facile two-step hydrothermal reaction, in which the untrathin Co-Mo-O nanosheets are connected to each other into a three-dimensional (3D) porous hierarchical architecture with Ni3S2 entrapped on the underneath Ni support. The resulting Co-Mo-O/Ni3S2/NF exhibits an excellent electrocatalytic activity for oxygen evolution reaction (OER) in KOH solution, which yields a 50 mA cm(-2 )of OER current density at an overpotential of 0.29 V, outperforming the state-of-the-art noble RuO2 (eta 50 = 0.42 V), Co-Mo-O/NF (eta 50 = 0.33 V) and Ni3S2/NF (eta 50 = 0.31 V). And it demonstrates a high specific capacity of 340 mAh g(-1) at 2 mA cm(-2) with good capability (82.1% of the retention at 32 mA cm(-2)) in basic solution when used as supercapacitor electrode, which is superior to those of Co-Mo-O/NF (183 mAh g(-1)) and Ni3S2/NF (70 mAh g(-1)). The outstanding electrochemical performance of Co-Mo-O/Ni3S2/NF is associated with the synergistic effect of the individual components as well as the nanosheets directly grown on Ni conducting support with more active sites exposed. Furthermore, Co-Mo-O/Ni3S2/NF displays good durability in 12 h-electrolysis experiment for OER and 10000 charge-discharge cycles. It is expected to benefit from Ni3S2 entrapped by the protective layer of 3D porous Co-Mo-O nanosheet arrays, which not only can provide channel for electrolyte ion to pass through, but also improve the stability of Ni3S2. In addition, the fabricated Co-Mo-O/Ni3S2/NF//Activated carbon (AC) asymmetrical supercapacitor shows an ultra-high energy density of 57.9 Wh kg(-1) at a power density of 1.1 kW kg(-1). (C) 2018 Elsevier Ltd. All rights reserved.