Over the years, selenium has caught the attention on its merits, high electronic conductivity, high melting point, and high energy capacity. Nevertheless, the enormous volumetric expansion and shuttle effects of polyselenides simultaneously hinder selenium application. We report a three-dimensional hierarchical structure composed of porous carbon layers derived from the metal-organic framework with Ni(OH)2 nanosheet shell as selenium host. The 3D hierarchical structure looks like slices of toast stacked on top of each other and decorated with Ni(OH)2 nanosheets. The toast improves the electronic conductivity of selenium and serves as a shelter to provide sufficient free space for volume change. The Ni(OH)2 nanosheet shell act as a functional protective barrier to restrain the shuttle effects and achieve a shorter ion transport path. Consequently, the Li–Se batteries deliver remarkable cyclic performance over 2500 cycles at 3 C with 0.018% capacity decay due to the unique structure. In addition, the electrode also performs well in Na–Se batteries.