A modified one step template self-assembly synthesis route was proposed to fabricate hollow sphere-like titanium nitride with high surface area. The synthesis features a high Mg ratio, NH₄Cl as the nitrogen precursor and a higher processing temperature. The final product was mainly hollow sphere-like TiN with a diameter of 100–280 nm and an average shell thickness of 25 nm. The specific surface area of the product was as high as 118.996 m² g⁻¹. A relatively detailed growth mechanism of these hollow structures was proposed in this manuscript.