The processes of (n)ZVI/AC（（nano）zero valent iron/activated carbon）micro-electrolysis were applied for nitrate removal from groundwater, aiming to reduce nitrate to N, an environmentally friendly end product. (n)ZVI was utilized and combined with selected commercial AC to form the micro-electrolysis. Effect of different operational parameters, including reductant dosage, (n)ZVI/AC ratios, and reaction pH, on nitrate and TN removal were cleared. The results showed that nZVI presents higher reaction activities than ZVI in micro-electrolysis. With the increase of the (n)ZVI/AC mass ration from 1:2 to 2:1, the TN removal increased from 16.8% to 38.9%, then declined with the further increase of the ratio. The nitrate removal was negatively correlated with the initial pH of the solution. Compared to ZVI particles, even with a lower dosage, nZVI presented 100% nitrate removal at acidic and neutral pH conditions, and TN removal could maintain higher than 35% with pH lower than 9.0. A kinetic model was also established to explain the pathways of nitrate removal, and the results indicated that AC not only enriched nitrate as an adsorbent but also present highly potential in catalytic converting nitrate to N. The technique presented great potentials in removing nitrate from water and a promising application prospect.