Magnesium-based alloys are widely used in the construction of automotive, aviation, and medical applications. The solutions presently used for the production of biodegradable materials are characterized by considerable energy consumption and limitations resulting from the use of different devices and technologies. The proposed material is easier to manufacture due to mechanical alloying (MA). Thanks to the MA process, it is possible to carefully tailor the desired chemical composition and microstructure. There are many parameters that can be modified during synthesis in order to obtain an alloy with the desired microstructure and specific expected alloy properties. The duration of grinding of the alloy, the size and number of balls, and the protective atmosphere have a great influence on the process of mechanical alloying and the properties of the obtained products. So, the aim of this work was to determine the influence of milling time on the phase composition and structure of Mg-based alloy synthesis products. The tested samples were milled for 5, 8, 13, 20, 30, 50, and 70 h. X-ray diffraction analysis (XRD) and scanning electron microscopy studies (SEM) with energy-dispersive spectroscopy (EDS) were performed to obtain the powder morphology and chemical composition of Mg66−xZn30Ca4Agx (where x = 1, 2) powders. Structure characterization based on the Rietveld refinement and crystallite size determination based on the Williamson–Hall theory of milling products were also carried out.