The extraction of gold (Ⅰ) cyanide in polyethylene glycol-based aqueous biphasic systems has been investigated. Almost all of gold (Ⅰ) cyanide was transferred into the PEG-rich phase from salt-rich phase. No influence of solution pH on gold (Ⅰ) cyanide extraction was observed. The gold (Ⅰ) cyanide in the PEG-rich phase can be easily reduced by zinc. The PEG-rich phase could be reused for extraction of gold (Ⅰ) cyanide with no decrease of extraction capability. The aqueous biphasic systems may provide a new technique for gold separation from cyanide solutions.