Low-temperature phase transitions in the EZ33A Mg-cast alloy have been investigated. Based on the structure assessment of the alloy after annealing at 150 °C (1826 h) and at 200 °C (2371 h) a grain boundary wetting transition by a second solid phase was documented. Within a 50 °C temperature range, substantial differences in the α(Mg) grain boundary fraction wetted by the (Mg,Zn)12RE intermetallic were observed. In contrast to what was reported in the literature, two different types of precipitates were found within α(Mg) grains. With increasing annealing temperatures, both types of precipitates dissolved.