Hydrogenated black TiO has been proven to tune the bandgap and utilize solar energy effectively. Herein, we report a facile strategy for controllably synthesizing stable mesoporous black TiO hollow spheres (MBTHSs) with a narrow bandgap via a template-free solvothermal approach combined with a small amine molecule reflux-encircling process and subsequent high-temperature hydrogenation, which are composed of highly crystalline pore-walls, Ti in frameworks and surface disorders.