Mesoporous titanium nitride (TiN) microspheres with tunable chamber structures were synthesized through NH3 nitridation of organotitania obtained via solvothermal alcoholysis. Owing to high content of organic species in organotitania, which stabilized the original structure and also promoted the nitridation at low temperature, TiN duplicated the solid, yolk–shell, and hollow chambers of organotitania in NH3 nitridation and also formed the mesoporous structure after removing organic species. During visible light-induced photocatalytic water splitting, the yolk–shell TiN demonstrated a higher H2 evolution efficiency than the solid, hollow, and crushed TiN; the yolk–shell TiN obtained through N2 nitridation; and other semiconductor photocatalysts reported so far without the aid of noble metals. This could be attributed mainly to the narrow energy band gap for absorbing visible light, high surface area, and excellent electrical conductivity, which facilitated light harvesting, reactant adsorption, and photoelectron–hole separation to suppress their recombination. Moreover, it could be easily recycled and thus used repetitively.