This paper explores the solvent extraction of KAu(CN)(2) from alkaline cyanide solutions using quaternary ammonium cetylpyridinium bromide (CPB) as an extractant with the addition of tributylphosphate (TBP) as a modifier. It also investigates the influence of several variables on gold extraction, including the molar ratio (beta) of CPB to Au(I), the volume percentage of TBP (phi(TBP)), NaCl concentration, phase ratio (AQ/ORG), and gold concentration in the aqueous phase. The results indicate that nearly all of the Au(I) (>98%) was transferred from the aqueous phase into the organic phase when beta = 1 and phi(TBP) = 30 vol%. We also carried out experiments for treating 20 L synthetic aurocyanide solution containing 10 mg/L Au(I) with column-shaped extraction equipment. The results demonstrated the recovery of more than 94.5% of Au(l) after two successive stages of extraction, and the Au(I) concentration in the raffinate was less than 0.5 mg/L. KSCN solution was used to strip the gold-loaded organic phase, and about 90% of Au(I) could be reverse extracted into the aqueous phase when the KSCN concentration reached 3.0 mol/L. The results obtained in this paper establish that the CPB/TBP extraction system has potential for practical application in the extraction and separation of gold from alkaline aurocyanide solutions. (C) 2009 Elsevier Ltd. All rights reserved.