Magnesium-based alloys are highly sought after in the industry due to their lightweight and reliable strength. However, the hexagonal crystal structure of magnesium results in the mechanical properties’ anisotropy. This anisotropy is effectively addressed by alloying magnesium with elements like zirconium, zinc, and rare earth metals (REM). The addition of these elements promotes rapid seed formation, yielding small grains with a uniform orientation distribution, thereby reducing anisotropy. Despite these benefits, the formation of intermetallic phases (IP) containing Zn, Zr, and REM within the microstructure can be a concern. Some of these IP phases can be exceedingly hard and brittle, thus weakening the material by providing easy pathways for crack propagation along grain boundaries (GBs). This issue becomes particularly significant if intermetallic phases form continuous layers along the entire GB between two neighboring GB triple junctions, a phenomenon known as complete GB wetting. To mitigate the risks associated with complete GB wetting and prevent the weakening of the alloy’s structure, understanding the potential occurrence of a GB wetting phase transition and how to control continuous GB layers of IP phases becomes crucial. In the investigation of a commercial magnesium alloy, ZEK100, the GB wetting phase transition (i.e., between complete and partial GB wetting) was successfully studied and confirmed. Notably, complete GB wetting was observed at temperatures near the liquidus point of the alloy. However, at lower temperatures, a coexistence of a nano-scaled precipitate film and bulk particles with nonzero contact angles within the same GB was observed. This insight into the wetting transition characteristics holds potential to expand the range of applications for the present alloy in the industry. By understanding and controlling GB wetting phenomena, the alloy’s mechanical properties and structural integrity can be enhanced, paving the way for its wider utilization in various industrial applications.