A photocatalyst of high-performance hierarchical nitrogen-doped MoS2 (N-MoS2) microsphere was fabricated by an in situ hydrothermal method in the presence of cetyltrimethylammonium bromide (CTAB). The as-prepared N-MoS2 microsphere was self-assembled by extremely thin interleaving petals, where CTAB acts as a nucleation site for the formation of the interleaving petals due to the strong interaction between CTA+ and [Formula: see text]. N-MoS2 showed higher N2 fixation ability (101.2 [Formula: see text] mol/g(cat)h) than the non-doped MoS2 under the visible light irradiation, and the improved photocatalytic activity could be ascribed to that the doped N narrows the band gap, and the surface reflecting and scattering effect caused by the hierarchical structure enhance the light adsorption. The trapping experiment of active species was also investigated to evaluate the role of photogenerated electrons in the photocatalytic reaction process. Meanwhile, the possible mechanism for the formation and excellent photocatalytic performance of N-MoS2 microsphere were also presented.