Heap bioleaching is regarded as an environmental-friendly technology to extract valuable metals, such as gold, silver, copper, etc., from low grade or waste ores. The chemical reactions accelerated by microorganisms are usually complex. Microbial activity is ascribed to the physiochemical factors such as temperature. Due to the variety of ore components, the thermal effect is difficult to elaborate. In this study, typical ores used for heap bioleaching of chalcopyrite are theoretically analyzed to explore the mechanism involving the thermal effect of chemical reactions. The thermal distribution is compared between different proportional combinations. The results show that biotite is the dominant contributor and should be verified carefully in the heap bioleaching of chalcopyrite.