Bifunctional heterogeneous catalytic processes for highly efficient removal of arsenic (As(III)) are receiving increased attention. However, the agglomerated nature and stability of nanoparticles are major concerns. Herein, we report a new process regarding the anchoring of CuFe₂O₄ nanoparticles on a substrate material, a kind of Fe–Ni foam, to form porous CuFe₂O₄ foam (CuFe₂O₄-foam) by in situ synthesis. The prepared material was then applied to activate peroxymonosulfate (PMS) for fast and efficient removal of As(III) from water. The results of removal experiments show that the complete removal of arsenic (<10 μg L⁻¹) from 1 mg L⁻¹ As(III) aqueous solution can be achieved within shorter time (<10 min) using this adsorbent coupled with PMS. The maximum adsorption capability of As(III) and As(V) on the prepared adsorbent is observed to be about 105.78 mg g⁻¹ and 120.32 mg g⁻¹, respectively. CuFe₂O₄-foam/PMS couple could work effectively in a wide pH range (3.0–9.0) and temperature range (10–60 °C), which is more beneficial to its application in actual water treatment engineering. The exhausted adsorbents can be refreshed for cyclic runs (at least 7 cycles) with insignificant capacity loss using alkaline solution as a regeneration strategy, suggesting this process has good stability. Investigation of the mechanism reveals that the route to the removal of As(III) is synchronous oxidation and sequestration in the arsenic removal process. The large As(III) removal capability and stability of CuFe₂O₄-foam/PMS show its potential as a promising candidate in real As(III)-contaminated groundwater treatment.