Electroless gold deposition is known to take place on Ni-based substrates even when the conventional reducing agent is excluded from the autocatalytic bath containing thiosulfate and sulfite as ligands for gold ions. It is shown in this paper that the reaction of gold deposition from this bath on electroless Ni-B substrate is not autocatalytic but, instead, proceeds primarily by the mechanism of substrate catalysis with galvanic displacement playing a secondary role. It was established that sulfite serves as the reducing agent for the substrate-catalyzed gold deposition reaction.