With increasing emphasis placed on cleaner chemical synthesis, energy efficiency and waste minimisation, the manufacture of pharmaceuticals and fine chemicals is undergoing a progressive shift from conventional stoichiometric organic processes to a harnessing of catalytic selectivity. In hydrogenation processes, gold catalysts have untapped potential in terms of selectivity in the reduction of a target functionality in multifunctional reactants. This Review provides a comprehensive evaluation of the catalytic applications of Au in hydrogenation, assessing the benefits relative to conventional transition metal (e.g. Pt, Pd and Ni) catalytic systems. Hydrogenation activity requires the formation of nanoscale Au particles that are (typically) anchored to oxide supports. The crucial catalyst structural and surface properties required to achieve enhanced hydrogenation performance in terms of rate, selectivity and stability are discussed. The synthesis procedures and characterisation methodologies directed at catalyst optimisation are evaluated. The practical application of Au catalysts is illustrated taking, as a case study, the hydrogenation of nitroaromatics, where critical features such as hydrogen adsorption/activation, structure sensitivity, metal-support interactions and active site characteristics are discussed. Commonality with the catalytic action of supported Ag is flagged with a consideration of the future outlook and direction for selective hydrogenation using Au catalysts.