Titanium dioxide (TiO2) materials are applied as electrode materials of Lithium-ion batteries in terms of good cycling stability. However, the poor lithium-ions batteries transport kinetics and low electronic conductivity limited the development of TiO2 as anode materials. As known, TiO2(B) is a metastable phase of titanium oxide and has better electrochemical performance than others. The crystal structure of TiO2(B) is comprised of edge and corner-sharing TiO6 octahedra which can lead to facile lithium-ion intercalation. In order to solve this problem, it is desirable to control the morphology of TiO2(B) to shorten the Li+ diffusion path. In this study, synthesized TiO2(B)/Anatase composite materials is deal anode materials for Lithium-ion batteries. The anatase makes the composite materials have long term stability. Because the anatase phase TiO2 has stable structure and it is hard to transform to other phases. Moreover, TiO2(B) provides the Li+ ion diffusion path to improve the electrochemical performance. Nowadays hydrothermal methods for the synthesis of TiO2(B) are the only reported. Herein, we report a new method to synthesize TiO2(B). The nanoparticles TiO2(B)/Anatase composite oxide can be successfully fabricated via a simple solid-state chemical reaction. The titanium oxysulfate sulfuric acid hydrate and oxalic acid are used as starting materials. The synthesis is processed with low-temperature solid-state reaction and then calcination. Compared to the traditional hydrothermal method, the synthesis process of solid-state chemical reaction is greener, simpler and eco-friendlier. This method has significant advantage in the field of nano materials synthesis. In this work, the uniformly TiO2(B)/Anatase microspheres are synthesized with a high crystalline. The synthesized TiO2(B)/Anatase displays good cycling stability and high capacity retention as an anode material for Lithium-ion batteries. This work provides a new idea for the future research of titanium oxide-based materials for anode materials.