The separation and recovery of Ni from the copper electrolyte by crystallization of nickel ammonium sulfate double salt were studied. It is found that the solubility of copper sulfate at the same temperature is less than that of nickel sulfate, while the solubility of copper ammonium sulfate is greater than that of nickel ammonium sulfate. So, by adding (NH₄)₂SO₄, the Ni can be selectively crystallized from the copper electrolyte. By adding (NH₄)₂SO₄ at the molar ratio of (NH₄)₂SO₄/NiSO₄ ≤0.8, and crystallizing at -15 °C for 10 h, the Ni in the copper electrolyte can be crystallized in the form of Ni(NH₄)₂(SO₄)₂×6H₂O. The qualified product of NiSO₄×6H₂O can be obtained by pyrolyzing the crystals, dissolving the pyrolysis product in water, and then concentrating the dissolved solution for crystallization. The method of double salt crystallization is a clean, environmentally-friendly, cost-effective and efficient method for separating and recovering nickel from copper electrolyte.