The role of iron in metal-bearing waste bioleaching was studied. Four various types of waste (printed circuit boards (PCBs), Ni-Cd batteries, alkaline batteries and Li-ion batteries) were treated by bioleaching using the acidophilic bacteria A. ferrooxidans and A. thiooxidans (separately or in mixture). Role of main leaching agents (Fe3+ ions or sulphuric acid) was simulated in abiotic experiments. Results showed that oxidation abilities of Fe3+ ions were crucial for recovery of Cu and Zn from PCBs, with the efficiencies of 88% and 100%, respectively. To recover 68% of Ni from PCBs, and 55% and 100% of Ni and Cd, respectively, from Ni-Cd batteries both oxidation action and hydrolysis of Fe3+ were required. The importance of Fe2+ ions as a reducing agent was showed in bioleaching of Co from Li-ion batteries and Mn from alkaline batteries. The efficiency of the processes has increased by 70% and 40% in Co and Mn bioleaching, respectively, in the presence of Fe2+ ions. Based on the results we suggest the integrated biometallurgical model of metal-bearing waste recycling in the effort to develop zero-waste and less energy-dependent technologies.