The aim of this paper was to attain defect free, pure copper castings with the highest possible electrical conductivity. In this connection, the effect of magnesium additives on the structure, the degree of undercooling (ΔTα = Tα-Tmin, where Tα – the equilibrium solidification temperature, Tmin – the minimum temperature at the beginning of solidification), electrical conductivity, and the oxygen concentration of pure copper castings have been studied. The two magnesium doses have been investigated; namely 0.1 wt.% and 0.2 wt.%. A thermal analysis was performed (using a type-S thermocouple) to determine the cooling curves. The degree of undercooling and recalescence were determined from the cooling and solidification curves, whereas the macrostructure characteristics were conducted based on a metallographic examination. It has been shown that the reaction of Mg causes solidification to transform from exogenous to endogenous. Finally, the results of electrical conductivity have been shown as well as the oxygen concentration for the used Mg additives.