A technique has been developed to electrodeposit gold directly on a molybdenum substrate without prior deposition of other metals. The electrodeposited gold films are adherent and protective against highly corrosive ambients. The process involves the formation of a porous oxide on the molybdenum substrate, deposition of gold into this oxide, and hydrogen reduction of the oxide. During the reduction of the oxide, the gold is mechanically trapped and the substrate in the vicinity of the molybdenum surface is converted to a two‐component gold‐molybdenum layer. This layer provides a suitable surface for further deposition.