We present a uniform rhombohedral Ni@ZnO bimetallic oxide host over carbon nanofibers (CNF) as an anode material for Li-ion batteries. Ni@ZnO was produced by annealing a Ni@zeolitic imidazolate framework (ZIF-8) hierarchically decorated over CNFs. The rationally-designed freestanding composite exhibited promising stability in electrochemical performance. A first reversible capacity of 1051 mA.h.g(-1) was measured at a current density of 100 mA.g(-1), and 88% of this capacity was retained after 100 cycles. We attribute this high capacity retention to the hierarchical structure of the Ni@ZnO-enwrapped carbon framework encapsulating the conductive CNFs, as demonstrated by scanning and transmission electron microscopy. The composite electrode also showed a high specific capacity of similar to 497 mA.h.g(-1) in high-rate testing at 1000 mA.g(-1), because the cage-like framework of the material allowed rapid charge transfer and Li-ion diffusion in the anode.