Hexachlorobenzene (HCB) is one of the most persistent environmental pollutants of global concern. Ni/Fe nanoparticles, with their small particle size, large surface area, and high reactivity, are a promising candidate for HCB degradation. In this work, we investigated the kinetics and products of the dechlorination of HCB by Ni/Fe nanoparticles and how the presence of heavy metal ions Cd(Ⅱ) and Zn(Ⅱ) influences the reaction. It is found that 400 μg/L HCB can be rapidly removed by 7.5 g/L Ni/Fe nanoparticles and the removal percentage reaches 99% in 48 h. The removal is facilitated by adsorption and sequential dechlorination of HCB, producing PCB, 1,2,3,4-TeCB, and 1,2,3-TCB as the main products, with 1,2,3,5/1,2,4,5-TeCB, 1,2,4-TCB, and 1,2-DCB as the minor products. The addition of heavy metal ions Cd(Ⅱ) and Zn(Ⅱ) does not significantly affect the removal rate of HCB but hinders the adsorption and degradation of the byproducts through competitive adsorption. Additionally, the concentration of both Cd(Ⅱ) and Zn(Ⅱ) decreases rapidly and achieves over 98% removal in 4 h. Our study reveals that Ni/Fe nanoparticles can remove HCB and heavy metals Cd(Ⅱ) and Zn(Ⅱ) concurrently, with the extent of HCB dechlorination reduced compared to that without heavy metal. These findings may inform the application of Ni/Fe nanoparticles in the treatment of water bodies and soil contaminated by both halogenated aromatics and heavy metal.