The new solvent extraction system for gold(Ⅰ) from alkaline cyanide solution by TBP with addition of surfactant in aqueous phase was studied. The effect of various factors, such as equilibrium pH, constitution of organic phase, molar ratio of CPB∶Au(CN)2-, extraction time, aqueous/organic phase ratio, different initial gold concentration, equilibrium temperature, different diluent, different types of extractants and surfactants etc., was inspected. The results show that gold(Ⅰ) can be extracted quantitatively by controlling the quantity of surfactant (CPB); both the equilibrium pH and diluent hardly influence percent extraction. Gold(Ⅰ) percent extraction reaches more than 98% under the optimal experimental conditions. 30% vol TBP diluted by sulphonating kerosene can load gold(Ⅰ) to rather high levels. Loading capacity is in excess of 38 g/L. The extraction mechanism is discussed and the overall extraction reaction is deduced.