In this contribution, the novel 2D sandwich-like NiO/C arrays on Ti foil are successfully designed and fabricated for the first time via simple and controllable hydrothermal process. In this strategy, we use green glucose as carbon source and ultrathin Ni(OH)2 nanosheet arrays as precursor for NiO nanoparticles and sacrificial templates for coupled graphitized carbon layers. This advanced sandwiched composite can not only provide large surface area for numerous active sites and continuous contact between active materials and electrolyte, but also protect the active nanoparticles from aggregation, pulverization and peeling off from conductive substrates. Furthermore, the porous structure derived from lots of substances loss under high-temperature calcinations can effectively buffer possible volume expansion and facilitate ion transfer. In this article, sandwiched NiO/C arrays, utilized as anode for LIBs, demonstrated high specific capacity (∼1458 mAh g−1 at 500 mA g−1) and excellent rate performance and cyclablity (∼95.7% retention after 300 cycles).