We reported the development of a new type of multifunctional titanium dioxide (TiO2)-graphene nanocomposite hydrogel (TGH) by a facile one-pot hydrothermal approach and explored its environmental and energy applications as photocatalyst, reusable adsorbents, and supercapacitor. During the hydrothermal reaction, the graphene nanosheets and TiO2 nanoparticles self-assembled into three-dimensional (3D) interconnected networks, in which the spherical nanostructured TiO2 nanoparticles with uniform size were densely anchored onto the graphene nanosheets. We have shown that the resultant TGH displayed the synergistic effects of the assembled graphene nanosheets and TiO2 nanoparticles and therefore exhibited a unique collection of physical and chemical properties such as increased adsorption capacities, enhanced photocatalytic activities, and improved electrochemical capacitive performance in comparison with pristine graphene hydrogel and TiO2 nanoparticles. These features collectively demonstrated the potential of 3D TGH as an attractive macroscopic device for versatile applications in environmental and energy storage issues.