To promote the engineering applications of high water backfill materials (HWBM) in mining, a series of experiments are performed to investigate the effects of the direct current (DC) electric field on the mechanic properties and electrical resistivity of HWBMs. Based on X-ray diffraction (XRD) and scanning electron microscopy (SEM) investigations, the influence of electrochemical treatment on the hydration products and the microstructure of the HWBM was studied. The results show that the peak strength, elastic modulus, deformation modulus and electrical resistivity of the HWBM samples all first increased and then decreased with the increasing of the potential gradient, and the peak points appeared when the potential gradient was 0.2 V/cm. The anisotropy of content of ettringite and calcium silicate hydrates (C–S–H) increased betweent the anodic and cathodic regions of samples. Meanwhile, microstructure in the anodic region of the samples was more stable after electrochemical treatment, which indicates that the different variation of mineralogical compositions and microstructures in different regions of the samples are the primary factors affecting the mechanic properties and electrical resistivity of the HWBM. Therefore, the electrochemical method is a potential technology to modify the engineering properties of the HWBM.