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Methyldimethylhydrazine and its by-products cause serious damage to human health. In this paper, Re3+-doped mesoporous TiO2 were synthesized for the photodegradation of UDMH. The structure, morphology and optical properties of photocatalyst were extensively characterized. The photocatalytic degradation was significantly enhanced, and 2%Nd-TiO2 showed the most excellent photocatalytic degradation performance with 93.3% degradation rate of UDMH. NDMA and FDMH were gradually and completely degraded. .O2- and·OH played an important role in the photocatalytic degradation of UDMH. The possible degradation pathways of UDMH analyzed by GC-MS. The work provided an effective method for the degradation of UDMH wastewater.