MoS2 hollow spheres with an average diameter of 165nm were prepared from Na2MoO4 and CH3CSNH2 at 82°C. A simple method was used to obtain smaller hollow spheres (70nm) without any complicated step, except for the addition of TiO2. The tribological properties of MoS2/TiO2 in rapeseed oil were studied using a four-ball tribometer under 350N at 0.383m/s. The effects of load and sliding velocity were also investigated. Wear was significantly alleviated by the produced lubricating film as lubricated with MoS2/TiO2, which was composed of MoO3, Fe2O3, Fe2(SO4)3, TiO2 (trace), and carbon-containing compounds. The tribological properties were also improved because of the decrease in the size of MoS2 and the synergistic effect between MoS2 and TiO2.