Bio-hydrometallurgical applications have been receiving more attention globally for processing of several metal bearing wastes. Developments in bioleaching enable this technique to be utilized as an alternative process for extraction of metals (ex-copper, gold, etc.) from complex ores or even concentrates, consequently solving several environmental issues. Organic and inorganic reagents or additives used during the process have been seen to affect the leaching efficiency of microbes for metal dissolution. The present review discusses the influence of certain organic–inorganic reagents and other materials or additives on the growth, oxidation activity, and bioleaching efficiency of acidophiles on metal dissolution.