The partition behaviour of Hg (II) was studied in an aqueous polyethylene glycol (PEG) - (NH4)2SO4 two-phase system as a function of halide, halide concentration, and pH. For a system prepared by mixing equal volumes of 40 % (w/w) PEG (1550) with 40 % (w/w) (NH4)2SO4, Hg(II) remains almost exclusively in the salt-rich phase. The addition of NaX (X = Cl−, Br−, I−) enhances Hg (II) partition into the PEG-rich phase due to the formation of halide complexes. The efficiency of halide extractants increases in the order: Cl− < Br− < I−. Mercury extraction is improved at lower halide ion concentration by higher stock salt solution acidity. From the distribution coefficients determined as a function of halide ion concentration, the extracted species were identified. The Hg (II) extractability is determined by the type and stability of the Hg (II) halide species, and depends on the stock salt solution acidity. The observed behaviour is discussed and a possible extraction mechanism is proposed.