Three-dimensional (3D) thin-film electrodes are promising solution to the volume change of active materials in lithium-ion batteries. As a conductive current collector, the 3D TiO2 nanotube array networks (TNAs) have a one-dimensional stable electronic conductive path and increase the adhesion between the current collector and raw material, thereby improving the cycle stability of active materials. In this study, a novel 3D-TNAs@Sb2S3 anode was fabricated by directly depositing natural stibnite onto 3D TNAs. The adhesion of Sb2S3 particles to the substrate was enhanced due to the large surface area provided by 3D-TNAs. Moreover, the porous layered structure composed of Sb2S3 nanoparticles relieved the stress generated during lithiation and adapted to the volume change of Sb2S3 during cycling. Therefore, the resulting composite anode exhibits high cycle and rate performance, reaching 0.36 mAh·cm−2 after 80 cycles at the galvanostatic rate of 1 mA·cm−2, with high coulombic efficiency of 98%.