The multi-ether compounds with different numbers of methoxy groups containing 1,3-dimethoxy-2,2-bis(methoxymethyl)propane and 1-methoxy-2,2-bis(methoxymethyl)butane were synthesized using the Williamson reaction from pentaerythritol and 1,1,1-tris(hydroxymethyl)propane, respectively, in the presence of sodium hydride and methyl iodide in tetrahydrofuran and they were characterized by 1H NMR, 13C NMR, and FTIR spectroscopy. These compounds were employed as external donors in the polymerization of propylene using the industrial Ziegler-Natta catalyst. A commercial spherical MgCl2-supported Ziegler-Natta catalyst containing diisobutyl phthalate as the internal donor was used for the polymerization of propylene. The role of ether compounds and industrial alkoxysilanes on the properties of polypropylene were studied using the xylene solubility method, melt flow index, gel permeation chromatography, scanning electron microscopy, and differential scanning calorimetry. The addition of the electron donors has led to improvements in the activity and selectivity of the Ziegler-Natta catalyst system.