The heterogeneous Ziegler-Natta (ZN) catalyst has detained the monopoly over industrial polypropylene (PP) production owing to its high activity and stereospecificity. It facilitates the production of a significant quantity of high-quality PP under mild reaction conditions and at a low cost. In its modern form, the catalyst consists of a pre-catalyst that involves TiCl4 supported on nanosized MgCl2, along with an organic Lewis basic modifier referred to as the internal donor (ID). This pre-catalyst becomes active with the introduction of alkylaluminum, often accompanied by an additional Lewis base called the external donor (ED). The inclusion of these donors marked a significant advancement in PP production, owing to a substantial improvement in both the stereospecificity and activity of the catalyst. In fact, using only TiCl4 by intrinsic characteristics of the catalyst, such as the multi-site, ill-defined, and air-sensitive nature, even though the situation has been gradually mitigated by recent advances.