The ductile to brittle transition temperature is a very important criterion that is used for selection of materials in some applications, especially in low-temperature conditions. For that reason, in this paper transition temperature of as-cast and austempered copper and copper–nickel alloyed ductile iron (DI) in the temperature interval from −196 to +150°C have been investigated. The microstructures of DIs and ADIs were examined by light microscope, whereas the fractured surfaces were observed by scanning electron microscope. The ADI materials have higher impact energies compared with DIs in an as−cast condition. In addition, the transition curves for ADIs are shifted towards lower temperatures. The fracture mode of Dls is influenced by a dominantly pearlitic matrix, exhibiting mostly brittle fracture through all temperatures of testing. By contrast, with decrease of temperature, the fracture mode for ADI materials changes gradually from fully ductile to fully brittle.