Aniline is one of the important organic chemical raw materials and is widely used in the chemical production industry, including dyes, pharmaceuticals, pesticides, explosives, spices, etc. At present, the yield and selectivity of aniline synthesis by direct amination are relatively low, and how to improve the catalytic efficiency has become an urgent problem to be solved. A series of Ti-V-MCM-41 catalysts with different silicon-titanium ratios was prepared by the hydrothermal synthesis method. According to the analysis of XRD, FT-IR, UV-vis DRS, BET, and SEM characterization of Ti-V-MCM-41, it was found that V-O-Si and Ti-O-Si were distributed on Ti-V-MCM-41. The direct photocatalysis amination of benzene and ammonia to aniline can be realized under mild conditions with this catalyst. The yield and selectivity of aniline were improved to 6.11% and 90.7%, respectively, by optimizing the synthesis and reaction conditions.