A multidisciplinary approach has been used to study Au occurrences within pyrite and arsenopyrite in four refractory Au ores from Colombia, France (Le Châtelet and Villeranges) and Portugal (Neves Norte). The Au was characterized by optical and scanning electron microscopy and analysed using electron and ion microprobes to determine Au distribution, with particular attention to spectral interferences in electron and ion microprobes, background measurements in electron probes, and quantitative analysis using external standardization in ion probes. The ionic emission rate is proven to be dependent on the Au status; combined Au has a greater ion emission than metallic Au. Invisible Au occurrences are closely linked to As distribution. Gold bonding in arsenopyrite, examined by transmission electron microscopy, is shown to be dispersed within the FeAsS crystal structure. Typical growth patterns and As-Au diffusion zoning in pyrite and arsenopyrite may account for the very irregular distribution of Au in these minerals.