A new type of TiO2-B nanoribbon anchored with NiO nanosheets (TiO2@NiO) is synthesized via a hydrothermal process and a subsequent homogeneous precipitation method. XRD analysis indicates that TiO2-B and cubic NiO phases exist in the composites. According to SEM images, the morphology of the TiO2@NiO hybrid material is unique, similar to that of leaf mosaic in biological systems. According to electrochemical investigations, the nanostructured hybrid material as an anode exhibits superior initial charge/discharge capacity and capacity retentions. The initial discharge capacity of the TiO2@NiO hybrid nanostructure is 395 mA h g−1, and the capacity remains 380 mA h g−1 after 50 charge/discharge cycles, which is about 96.2% capacity retention and 7.8% higher than that of pristine TiO2-B nanoribbons.