The electrochemistry of leaching gold with thiosulphate has been studied systematically by using electrochemical techniques. Results show that the current peak of anodic dissolution of gold occurs at about 50 mV(SCE) and there is passivation in the polarisation curve in the thiosulphate solution in the absence of ammonia. Ammonia markedly improves the anodic dissolution rate of gold and reduces the passivation as well as making the current peak shift negatively. Results also show that there is no current peak for a cathodic process in the range of 0 -900 mV(SCE) in the thiosulphate solution in the presence of oxygen but absence of cupric ions and ammonia. In the solution containing 0. 1 mol/L cupric-ammonia ions, the peak occurs at about -400 mV (SCE) and the cathodic process is characteristic of a catalytic reaction. Oxygen presents a predominate effect on the cathodic process. Based on the electrochemical investigation, the following mechanism of leaching gold with ammoniacal thiosulphate has been proposed. Ammonia reacts primarily with gold ions on th anodic surface of gold and the formed A (NH3)2+ rea~s then with S2O 3 in solution to form the stabler Au(S203) 2 . Cu (NHS) 4 gains electrons on the cathodic surface and is reduced to CU(N) ? which is then oxidised by oxygen and regenerated into Cu(NH3) 4 after entering the solution.