Nb₂O₅ is introduced to act as a novel carrier of CuO using for Hg⁰ removal, presenting the excellent performance compared to niobium combined with other metal oxides (MnO₂, CeO₂, Fe₂O₃). By regulating the calcination temperature and CuO load amount, it was found that the formative stage of CuNb₂O₆ was the optimum binding degree of CuO and Nb₂O₅, which was beneficial for strong interaction of active component and carrier. Hg⁰ removal behaviors showed Cu_0.5/Nb₂O₅ exhibited the high Hg⁰ adsorption capacity, about 0.32 mg/g for 200 min at 150 ℃, and had a wide temperature range (100–250 ℃). SO₂ and H₂O have slight toxic effects on Hg⁰ capture, while O₂ plays an important role in Hg⁰ capture. Studies on the structure and properties of samples manifested CuO was homogeneously dispersed on the surface of Nb₂O₅, and Cu_0.5/Nb₂O₅ had good thermal stability and abundant surface acid property, besides, Cu⁺ specie can be more easily generated, which was beneficial for Hg⁰ removal in the flue gas. Furthermore, the removal mechanism of Hg⁰ was also studied, manifested Cu_0.5/Nb₂O₅ can be considered as a promising mercury adsorbent for various applications.