Mixed-valent iron mineral has significant effects in redox reaction and engineering applications. Magnetite (Fe3O4) combined with zero-valent iron (ZVI) were chosen to reduce N-nitrosodimethylamine (NDMA). Enhancement had been shown in ZVI-Fe3O4 system than the sum of removals of ZVI and Fe3O4 systems. Lower solution pH value facilitated the removal of NDMA, the concentration of dissolved oxygen (DO) had little effect. The main reduction products of NDMA by ZVI-Fe3O4 were 1,1-dimethylhydrazine (UDMH) and dimethylamine (DMA). The total nitrogen mass was unbalanced. By capturing the active species in the ZVI-Fe3O4 system, active hydrogen atoms had been determined. Catalytic hydrogenation was proposed to be the mechanism. Electrochemical tests showed that ZVI-Fe3O4 had a lower open circuit potential and a higher corrosion current than ZVI, the presence of Fe3O4 promoted the corrosion of ZVI. Scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses of solid powders showed that the corrosion was more serious and no other substances were formed on the surface of powders in ZVI-Fe3O4 system after reaction. X-ray photoelectron spectroscopy (XPS) showed that the value of ratio of peak area of Fe(III) to Fe(II) of ZVI-Fe3O4 surfaces was lowest. The Fe(III) on the powders’ surface could be reduced by ZVI and the surface passivation of ZVI would be prevented, which would be benefit for the generation of active hydrogen atoms.