A detailed characterization of an iron oxy/hydroxide (gossan type) bearing refractory gold/silver ore was performed with a new diagnostic approach for the development of a pretreatment process prior to cyanide leaching. Gold was observed to be present as native and electrum (6 24 mu m in size) and associated with limonite, goethite and lepidocrocite within calcite and quartz matrix. Mineral liberation analysis (MLA) showed that electrum is found as free grains and in association with beudantite, limonite/goethite and quartz. Silver was mainly present as acanthite (Ag2S) and electrum and as inclusions within beudantite phase in the ore. The cyanide leaching tests showed that the extractions of gold and silver from the ore (d(80): 50 mu m) were limited to 76% and 23%, respectively, over a leaching period of 24 h. Diagnostic leaching tests coupled with the detailed mineralogical analysis of the ore suggest that the refractory gold and silver are mainly associated within iron oxide mineral phases such as limonite/goethite and jarosite-beudantite, which can be decomposed in alkaline solutions. Based on these characterizations, alkaline pretreatment of ore in potassium hydroxide solution was performed prior to cyanidation, which improved significantly the extraction of silver and gold up to 87% Ag and 90% Au. These findings suggest that alkaline leaching can be used as a new diagnostic approach to characterize the refractoriness of iron oxy/hydroxide bearing gold/silver ore and as a pretreatment method to overcome the refractoriness.