The rational design and controllable synthesis of strongly coupled inorganic/graphene hybrids represents a long-standing challenge to develop advanced catalysts and energy storage materials. Here, we report a simple sol-gel method towards creating ultra-dispersed TiO2 nanoparticles on graphene with an unprecedented degree of control based on the precise separation and manipulation of nanoparticle nucleated, grown, anchored and crystallized, and the reduction of graphene oxide (GO), respectively. The hybrid materials show ultra-dispersed small anatase nanoparticles (~ 5 nm), ultra-thin thickness (≤ 3 layers) and a high surface area of 229 m2/g, and exhibit a high specific capacity of 94 mAhg-1 at ~ 59 C, which is twice as that of mechanically mixed composites (41 mAhg-1), demonstrating the potential of strongly synergistic coupling effects for advanced functional systems.