It is urgently desired to develop a promising method for deep removal of vanadium from molybdate solution for the efficient recycle of spent hydrodesulfurization (HDS) catalyst. In this paper, a novel method was investigated to deeply remove vanadium using γ-Fe₂O₃ particles as adsorbent. The properties of synthesized adsorbent were analyzed by a series of characterization methods. The adsorbent composed of γ-Fe₂O₃ nanoparticles with a diameter of 10–15 nm shows superparamagnetism and the saturation magnetization is about 56 emu·g⁻¹. The performance of this adsorbent including the vanadium removal efficiency and adsorbent stability was evaluated. The vanadium removal rate is up to 97.6% and the co-adsorbed Mo is lower than 5% at a pH of 10 within only 30 min. Furthermore, both magnetism and adsorption capacity of the γ-Fe₂O₃ adsorbent are nearly unchanged after 30 days storage. The adsorption mechanism was revealed that polymeric vanadium ions exhibit higher affinity with γ-Fe₂O₃ than MoO₄²⁻, and the adsorption follows ion exchange mechanism between hydroxyls covered on the adsorbent. The γ-Fe₂O₃ adsorbent presents a series of advantages of excellent V-removal performance, good recyclability, excellent stability, which may have significant potential for industrial-scale applications.