Metal-organic frameworks (MOFs) appear as interesting candidates for various applications. Herein, we report the growth of Ni-based MOF nanosheets on a flexible carbon cloth substrate as a binder-free anode. Furthermore, unique core-shell Co3O4/Ni-based MOFs are successfully anchored on a carbon cloth substrate by a facile two-step hydrothermal method. The as-prepared hybrid materials are directly used as electrode materials without adding any nonelectroactive components such as the insulating binders or conductive additive, which exhibit an excellent specific capacity (209 mAh g−1 at 1.0 A g−1) and a good cycling stability (90% retention after 3000 cycles). In addition, triethanolamine (TEOA)-assisted Ni-based MOF can be used as a photocatalyst for hydrogen evolution from water splitting under the near-infrared irradiation (λ > 800 nm). The present results reveal a potential prospect for the Co3O4/Ni-based MOFs in the field of energy storage and the near-infrared driven photocatalyst.