Photodriven nonoxidative coupling of CH₄ (NOCM) is an attractive potential way to use abundant methane resources. Herein, an n‐type doped photocatalyst for NOCM is created by doping single‐atom Nb into hierarchical porous TiO₂–SiO₂ (TS) microarray, which exhibits a high conversion rate of 3.57 μmol g⁻¹ h⁻¹ with good recyclability. The Nb dopant replaces the 6‐coordinated titanium on the (1 0 1) plane and forms shallow electron‐trapped surface polarons along [0 1 0] direction and the comparison of different models proves that the electron localization caused by the n‐type doping is beneficial to both methane activation and ethane desorption. The positive effect of n‐type dopant on CH₄ conversion is further verified on Mo‐, W‐ and Ta‐doped composites. In contrast, the doping of p‐type dopant (Ga, Cu, Fe) shows a less active influence.