Electrochemical gold deposition from sulfite solutions was studied by means of voltammetry, EIS and EQCM. A gold film electrode was used for polyaniline layer formation by electrochemical oxidation of aniline. The standard electrochemical reduction potential of the reaction [Au(SO3)2]3− + e− = Au + 2 SO32− was determined, and is equal to 0.116 V (vs. NHE). Both solution stirring and temperature increase accelerate the electrochemical reduction of gold, when the electrode potential is below −0.55 V. When the potential is above −0.55 V the electrochemical reduction proceeds via passive layer formation. Our study suggests that the passive layer consists of chemically adsorbed sulfite ions and sulfur. The gold film deposited from sulfite solution is a high quality substrate suitable for conducting polymer layer formation. This technique, where a polymer layer electrode is prepared by thin gold film deposition onto a metal surface and by subsequent polymer layer formation, can be applied in sensor research and technology.