The solar-driven water splitting for the production of renewable green hydrogen fundamentally relies on the exploration of efficient photocatalysts. Nanostructured TiO₂ is widely recognized as a promising material for photocatalysis, yet it remains hindered by inadequate light harvesting and fast photogenerated carrier recombination. Herein, calcined C/TiO₂ xerogels with yolk–shell and core–shell nanostructures (denoted as YS-C/TiO₂ and CS-C/TiO₂) were designed and fabricated via a typical sol–gel–calcination assisted approach. Thanks to the encapsulation of carbon nanospheres into TiO₂, it effectively enhances light absorption, improves carrier separation, and lessens carrier recombination, making the well-designed YS-C/TiO₂ composite display a remarkable hydrogen evolution rate of 975 µmol g⁻¹ h⁻¹ under simulated solar light irradiation and without the use of any co-catalyst, which is approximately 21.7 times that of the commercial TiO₂. The work provides an efficacious design concept in developing nanostructured TiO₂-based photocatalysts and in boosting broad photocatalytic applications.