A study has been performed to select optimum process conditions (temperature, pH, reagent concentration, reaction kinetics, deposition time, etc.) in gold deposition on Si(n) from sulphite/thiosulphate electrolytic baths. Gold deposits have been obtained by electrochemical techniques such as constant potential, constant current, cyclic voltammetry and pulsating overpotential, in diffusional regime or by charge transfer control, at two pH values (6 and 9) and two temperatures (30 and 50 A degrees C). The surface morphology of the Au deposits was studied by scanning electron microscopy (SEM), the preferred orientation and average size of the Au electrodeposited particles on n-Si substrates were obtained by X-ray diffraction (XRD), and qualitative and semiquantitative analysis of the gold sample was performed by energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS). The surface sulphur content was much lower or almost zero for gold samples obtained at pH 9 compared to those obtained at pH 6. However, when the different methods were compared at pH 6, both cyclic voltammetry and pulsating overpotential deposition led to deposits with a low or zero sulphur content. The results also show that various morphologies with different grain sizes can be obtained without the addition of additives.