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MWNTs/Fe2O3 was prepared by chemical liquid-deposition process, and unsymmetrical dimethylhydrazine (UDMH) wastewater was chosen as targets to evaluate the photocatalytic performance of MWNTs/Fe2O3. Mechanism of MWNTs in MWNTs/Fe2O3 composites was investigated by XRD, TEM, UV-vis,FTIR, TG-DSC and Raman spectra. The results demonstrate that MWNTs will influence the absorbability and the ability of photocatalysis of Fe2O3. When the mass ratio between MWNTs and Fe2O3 is 1:2, the decomposition efficiency of Fe2O3 photocatalysis for UDMH will be increased effectively. There is a quantitative relationship between the amount of MWNTs and the crystal type of Fe2O3. When the mass ratio between MWNTs and Fe2O3 is higher than 5:1, Fe2O3 will be transformed from α to γ. The introduction of MWNTs has broad the light effect of Fe2O3. The close connection between MWNTs and Fe2O3 form a positive interaction and a strong combination, during which they also produce a chemical bond of Fe-O-C. Under the light, MWNTs will work as a photosensitizer and transform electrons to the Fe2O3 through Fe-O-C, which reduce the possibility of electron-hole pairs recombination and increase the efficiency of photocatalysis.