Hollow structure TiO2 were prepared by solvothermal method based on carbon spheres as templates, and TiO2/S composite for Li-S battery cathode material was achieved after combined with element sulfur vis liquid infiration method. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA) were used to characterise the morphological structure and to determine the component content. Cyclic voltammetry (CV), Electrochemical impedance spectroscopy (EIS), Galvanostatic charge-discharge were used to analyse the electrochemical performances of products. The results reveal that elemental sulfur was infiltrated into hollow TiO2 successfully. Besides, TiO2 not only enhanced electronic conductivity of sulfur, effectively controlled the use of elemental sulfur, but also mitigated the “ shuttle effect ” from polysulfides. So, the coulomb efficiency and cycle performance were greatly improved.